JP2019532129A - Polycyclic glyoxylates as photoinitiators - Google Patents

Abstract

The present invention relates to formula (1) wherein X is O, S or a direct bond, Y is O, S or CR9R10, R1, R2, R3, R4, R5, R6, R7 and R8. Independently of one another, hydrogen, halogen, C1-C18 alkyl, C5-C10 cycloalkyl, C2-C18 alkenyl, phenyl, C1-C4 alkoxy, C5-C7 cycloalkoxy, phenoxy, C1-C4-alkylthio, C5- C7 cycloalkylthio, phenylthio, di (C1-C4 alkyl) amino, di (C5-C7 cycloalkyl) amino, N-morpholinyl, N-piperidinyl or a group of formula (2) provided that R1, R2, R3, One or more of R4, R5, R6, R7 or R8 is a group of formula (2) and R9, R10 are independently of each other. Hydrogen, C1-C18 alkyl, C2-C12 alkenyl, C5-C10 cycloalkyl, phenyl-C1-C4 alkyl, phenyl, or 5-, 6-, or 7-membered with the C atom to which they are attached Forming a ring and R11 is hydrogen, C1-C18 alkyl, C5-C10 cycloalkyl, C2-C12 alkenyl, phenyl-C1-C4 alkyl or phenyl). [Chemical 1] [Selected figure] None

Description

  The object of the present invention is novel polycyclic photoinitiators and their use for the polymerization (curing) of radically polymerizable compositions induced by electromagnetic radiation.

  The present inventors have now discovered that polycyclic glyoxylate represents a highly efficient novel photoinitiator with low volatility and excellent curing properties. The photoinitiator of the present invention can induce curing of the radical polymerizable composition by irradiation from various radiation sources. However, one particular advantage of the photoinitiator according to the present invention is that good curing properties can be achieved even when providing electromagnetic radiation by means of a light emitting diode (LED).

  Surprisingly, photoinitiators in which one or more glyoxylate functional groups are attached to a polycyclic aromatic or heteroaromatic system are the subject of the present invention.

（式中、
Ｘは、Ｏ、Ｓまたは直接結合であり、
Ｙは、Ｏ、ＳまたはＣＲ_９Ｒ_１０であり、
Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７およびＲ_８は、互いに独立して、水素、ハロゲン、Ｃ_１−Ｃ_１８アルキル、Ｃ_５−Ｃ_１０シクロアルキル、Ｃ_２−Ｃ_１８アルケニル、フェニル、Ｃ_１−Ｃ_４アルコキシ、Ｃ_５−Ｃ_７シクロアルコキシ、フェノキシ、Ｃ_１−Ｃ_４−アルキルチオ、Ｃ_５−Ｃ_７シクロアルキルチオ、フェニルチオ、ジ（Ｃ_１−Ｃ_４アルキル）アミノ、ジ（Ｃ_５−Ｃ_７シクロアルキル）アミノ、Ｎ−モルホリニル、Ｎ−ピペリジニルまたは式（２）の基

であり、但し、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７またはＲ_８のうちの１つまたは１つより多くは式（２）の基であり、
Ｒ_９、Ｒ_１０は独立して、水素、Ｃ_１−Ｃ_１８アルキル、Ｃ_２−Ｃ_１２アルケニル、Ｃ_５−Ｃ_１０シクロアルキル、フェニル−Ｃ_１−Ｃ_４アルキル、フェニルであるか、またはそれらが結合するＣ原子と一緒に５員環、６員環もしくは７員環を形成し、
Ｒ_１１は、水素、Ｃ_１−Ｃ_１８アルキル、Ｃ_５−Ｃ_１０シクロアルキル、Ｃ_２−Ｃ_１２アルケニル、フェニル−Ｃ_１−Ｃ_４アルキルまたはフェニルである）
の光開始剤化合物である。 They have the formula (1)

(Where
X is O, S or a direct bond,
Y is O, S or CR ₉ R ₁₀ ;
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, halogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₈ alkenyl, _phenyl, C 1 -C _{4 alkoxy,} C 5 -C ₇ cycloalkoxy, _phenoxy, C 1 -C ₄ - _alkylthio, C 5 -C ₇ cycloalkylthio, phenylthio, di _(C 1 -C ₄ alkyl) amino, di _(C 5 -C ₇ cycloalkyl) amino, N- morpholinyl, N- piperidinyl, or a group of formula (2)

Provided that one or more of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2);
R ₉ and R ₁₀ are independently hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₀ cycloalkyl, phenyl-C ₁ -C ₄ alkyl, phenyl, or Forms a 5-membered ring, 6-membered ring or 7-membered ring with the C atom to which
R ₁₁ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₂ alkenyl, phenyl-C ₁ -C ₄ alkyl or phenyl)
Of the photoinitiator compound.

In some embodiments of the invention, the following compounds are excluded:

Of interest are compounds of formula (1), where
(I) _one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2), or (ii) R ₁ , R ₂ , One of R ₃ or R ₄ is a group of formula (2), and one of R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2);
R ₉ , R ₁₀ and R ₁₁ are as defined above.

Of particular interest are compounds of formula (1), where
(I) _one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2), or (ii) R ₁ , R ₂ , One of R ₃ or R ₄ is a group of formula (2), and one of R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2);
R ₉ and R ₁₀ are independently hydrogen, C ₁ -C ₁₈ alkyl, or together with the C atom to which they are attached, form a 5-, 6-, or 7-membered ring;
R ₁₁ is C ₁ -C ₁₈ alkyl.

Particularly preferred are compounds of formula (1), wherein
(I) _one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2), or (ii) R ₁ , R ₂ , One of R ₃ or R ₄ is a group of formula (2), and one of R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2);
R ₉ and R ₁₀ are independently hydrogen or methyl;
R ₁₁ is methyl or ethyl.

Further emphasized are compounds of formula (1) above, wherein the remaining groups R _{1 to} R ₄ and R _{5 to} R ₈ are independently hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C _{4. alkoxy,} C 1 -C ₄ alkylthio, N- morpholinyl or N- piperidinyl.

In particular, the remaining groups R _{1 to} R ₄ and R _{5 to} R ₈ are hydrogen.

C ₁ -C ₁₈ alkyl is linear or branched, for _example, C 1 -C ₆ - is or _C 1 -C ₄ -alkyl. Examples are methyl, ethyl, propyl, isopropyl, 1-methylpropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, 2,2-dimethylpropyl, hexyl, heptyl, 2,4,4-trimethyl Phenyl, 2-ethylhexyl or n-octyl. C ₁ -C ₄ alkyl has the same meaning as given above up to the corresponding number of C atoms.

C ₅ -C ₇ cycloalkyl is, for example, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or tricycle [3.3.1.1 ^3,7 ] dec-2-yl, especially cyclopentyl and cyclohexyl, preferably cyclohexyl. is there. C ₁ -C ₄ alkoxy is a linear or branched, for example, methoxy, ethoxy, propoxy, isopropoxy, n- butyloxy, sec- butyloxy, iso - butyloxy or tert- butyloxy, especially methoxy. C ₅ -C ₇ cycloalkoxy is C ₅ -C ₇ cycloalkyl-O—, wherein C ₅ -C ₇ cycloalkyl is defined as given above.

C ₂ -C ₁₈ alkenyl group, mono- or polyunsaturated, linear or branched, for _{example, C 2 -C 8 -, C} 2 -C 6 - is or _C 2 -C ₄ alkenyl. Examples are allyl, methallyl, vinyl, 1,1-dimethylallyl, 2-propen-1-yl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentadienyl, 5-hexenyl, 1-ethenylhexyl. Or 7-octenyl, especially allyl or vinyl.

C ₁ -C ₄ alkylthio is linear or branched, for example, methylthio, ethylthio, propylthio, isopropylthio, n- butylthio, sec- butylthio, isobutylthio or tert- butylthio, preferably methylthio.

C ₁ -C ₄ alkyl and C ₅ -C ₇ cycloalkyl in the terms di (C ₁ -C ₄ alkyl) amino, C ₅ -C ₇ cycloalkylthio, and di (C ₅ -C ₇ cycloalkyl) amino are: Has the same meaning as given above.

  Halogen is fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine, preferably fluorine and chlorine.

のような構造が形成される。 R ₉ and R ₁₀ together with the C atom to which they are attached form a 5-, 6- or 7-membered ring, preferably a saturated ring, for example

The following structure is formed.

（式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７およびＲ_８は、互いに独立して、水素、ハロゲン、Ｃ_１−Ｃ_１８アルキル、Ｃ_５−Ｃ_１０シクロアルキル、Ｃ_２−Ｃ_１８アルケニル、フェニル、Ｃ_１−Ｃ_４アルコキシ、Ｃ_５−Ｃ_７シクロアルコキシ、フェノキシ、Ｃ_１−Ｃ_４−アルキルチオ、Ｃ_５−Ｃ_７シクロアルキルチオ、フェニルチオ、ジ（Ｃ_１−Ｃ_４アルキル）アミノ、ジ（Ｃ_５−Ｃ_７シクロアルキル）アミノ、Ｎ−モルホリニル、Ｎ−ピペリジニルまたは式（２）の基であり、但し、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７またはＲ_８のうちの１つまたは１つより多くは式（２）の基であり、
Ｒ_９、Ｒ_１０は独立して、水素、Ｃ_１−Ｃ_１８アルキル、Ｃ_２−Ｃ_１２アルケニル、Ｃ_５−Ｃ_１０シクロアルキル、フェニル−Ｃ_１−Ｃ_４アルキル、フェニルであるか、またはそれらが結合するＣ原子と一緒に５員環、６員環もしくは７員環を形成し、
Ｒ_１１は、水素、Ｃ_１−Ｃ_１８アルキル、Ｃ_５−Ｃ_１０シクロアルキル、Ｃ_２−Ｃ_１２アルケニル、フェニル−Ｃ_１−Ｃ_４アルキルまたはフェニルである）
である。 In certain embodiments, the compound has formula (3)

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, halogen, C ₁ -C ₁₈ alkyl, C ₅ -C _{10. cycloalkyl,} C 2 _{-C 18} alkenyl, _phenyl, C 1 -C _{4 alkoxy,} C 5 -C ₇ cycloalkoxy, _phenoxy, C 1 -C ₄ - _alkylthio, C 5 -C ₇ cycloalkylthio, phenylthio, di (C ₁ -C ₄ alkyl) amino, di _(C 5 -C ₇ cycloalkyl) amino, N- morpholinyl, N- piperidinyl, or a group of formula (2), _{where, R 1, R 2, R} 3, R 4 , R ₅ , R ₆ , R ₇ or R ₈ are more than one group of formula (2),
R ₉ and R ₁₀ are independently hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₀ cycloalkyl, phenyl-C ₁ -C ₄ alkyl, phenyl, or Forms a 5-membered ring, 6-membered ring or 7-membered ring with the C atom to which
R ₁₁ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₂ alkenyl, phenyl-C ₁ -C ₄ alkyl or phenyl)
It is.

More preferred are compounds of formula (3), wherein
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, halogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, phenyl or A group of formula (2), wherein one or more of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R ₈ is of formula (2) Group,
R ₉ and R ₁₀ are independently hydrogen, C ₁ -C ₁₈ alkyl, or together with the C atom to which they are attached form a 5-, 6-, or 7-membered ring;
R ₁₁ is C ₁ -C ₁₈ alkyl or C ₂ -C ₁₂ alkenyl.

Also preferred are compounds of formula (3), wherein
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen or a group of formula (2);
Provided that one or more of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2);
R ₉ and R ₁₀ are independently hydrogen or C ₁ -C ₁₈ alkyl;
R ₁₁ is C ₁ -C ₁₈ alkyl.

Also particularly preferred are compounds of formula (3), wherein
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen or a group of formula (2);
Provided that one or more of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2);
R ₉ and R ₁₀ are independently hydrogen or methyl;
R ₁₁ is methyl or ethyl.

（式中、
Ｘは、Ｏ、Ｓまたは直接結合であり、
Ｙは、Ｏ、ＳまたはＣＲ_９Ｒ_１０であり、
Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７およびＲ_８は、互いに独立して、水素、ハロゲン、Ｃ_１−Ｃ_４アルキル、Ｃ_５−Ｃ_７シクロアルキル、Ｃ_２−Ｃ_１８アルケニル、フェニル、Ｃ_１−Ｃ_４アルコキシ、Ｃ_５−Ｃ_７シクロアルコキシ、フェノキシ、Ｃ_１−Ｃ_４−アルキルチオ、Ｃ_５−Ｃ_７シクロアルキルチオ、フェニルチオ、ジ（Ｃ_１−Ｃ_４アルキル）アミノ、ジ（Ｃ_５−Ｃ_７シクロアルキル）アミノ、Ｎ−モルホリニル、Ｎ−ピペリジニルまたは式（２）の基であり、但し、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７またはＲ_８のうちの１つまたは１つより多くは式（２）の基であり、
Ｒ_９、Ｒ_１０は独立して、水素、Ｃ_１−Ｃ_１８アルキル、Ｃ_２−Ｃ_１２アルケニル、Ｃ_５−Ｃ_１０シクロアルキル、フェニル−Ｃ_１−Ｃ_４アルキル、フェニルであるか、またはそれらが結合するＣ原子と一緒に５員環、６員環もしくは７員環を形成し、
Ｒ_１１は、水素、Ｃ_１−Ｃ_１８アルキル、Ｃ_５−Ｃ_１０シクロアルキル、Ｃ_２−Ｃ_１２アルケニル、フェニル−Ｃ_１−Ｃ_４アルキルまたはフェニルであり、
但し、

は除外される）
に関する。 The present invention also provides a compound of formula (1)

(Where
X is O, S or a direct bond,
Y is O, S or CR ₉ R ₁₀ ;
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, halogen, C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl, C ₂ -C ₁₈ alkenyl, _phenyl, C 1 -C _{4 alkoxy,} C 5 -C ₇ cycloalkoxy, _phenoxy, C 1 -C ₄ - _alkylthio, C 5 -C ₇ cycloalkylthio, phenylthio, di _(C 1 -C ₄ Alkyl) amino, di (C ₅ -C ₇ cycloalkyl) amino, N-morpholinyl, N-piperidinyl or a group of formula (2) provided that R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , One or more of R ₆ , R ₇ or R ₈ is a group of formula (2);
R ₉ and R ₁₀ are independently hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₀ cycloalkyl, phenyl-C ₁ -C ₄ alkyl, phenyl, or Forms a 5-membered ring, 6-membered ring or 7-membered ring with the C atom to which
R ₁₁ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₂ alkenyl, phenyl-C ₁ -C ₄ alkyl or phenyl;
However,

Are excluded)
About.

It is a figure which shows the polymerization heat and glass transition temperature of the obtained polymer.

  The term “and / or” or “or / and” in this context is not only one of the defined options (replacement), but also some of the defined options (replacement), ie a mixture of different options (replacement). Means that both may exist together.

  The term “optionally substituted” means that the group it describes is either unsubstituted or substituted.

  The term “at least” is meant to define one or more than one, for example one or two or three, preferably one or two.

  Throughout this specification and the appended claims, unless the context requires otherwise, the word “comprise”, or “comprises” or “comprising”, etc. Variations are meant to include the stated integers or steps or integers or groups of steps, but are not understood to exclude any other integers or steps or groups of integers or steps.

  In the context of this application, the term “(meth) acrylate” is meant to refer to acrylate and the corresponding methacrylate.

  The choices indicated above for the compounds according to the invention in the context of the present invention are intended to refer to all categories of claims as well, ie claims of composition, use, method as well.

  The present invention is not limited to the particular compounds, configurations, method steps, substrates, and materials disclosed herein, and such compounds, configurations, method steps, substrates, and materials may vary somewhat. I want you to understand. Also, the terminology used herein is used for the purpose of describing particular embodiments only, as the scope of the present invention is limited only by the appended claims and equivalents thereof, It should also be understood that it is not intended to be limiting.

  As used herein and in the appended claims, the singular forms “a (a), (an)” and “the” are plural unless the context clearly dictates otherwise. Please note that the target object is included.

  Unless otherwise defined, any terms and scientific terms used herein are intended to have the meanings commonly understood by one of ordinary skill in the art to which this invention pertains.

  The compounds of the present invention can be made by well-established methods for the synthesis of arylglyoxylates.

  One non-limiting possibility is the Friedel-Crafts acylation of polycyclic compounds with the appropriate oxoacetate derivatives (eg chlorooxoacetate or oxalate) Comprising obtaining a-, di- or poly-glyoxylated polycyclic compound. Friedel-Crafts acylation in polycyclic aromatic systems relevant to the present invention is well known. These glyoxylations by Friedel-Crafts acylation reactions can be regioselective or give a mixture of regioisomers. For example, the glyoxyl oxidation of dibenzofuran proceeds regioselectively to give 2-glyoxylate- or 2,8-diglyoxylate derivatives (Bocknack, B.M. et al., Tetrahedron (2005), 61 (26 ), 6266-6575).

Regioselective glyoxyl oxidation has also been reported to occur with thianthrene to obtain 2-glyoxylate derivatives (see Kura, H. et al., PCT Int. Appl., 2000052530, September 8, 2000). thing).

On the other hand, mixtures of 2- and 3-monoacyl- or 2,7- and 2,8-diacyl derivatives are obtained by Friedel-Crafts acylation of phenoxathiin (see, for example, Coic, JP et al., Journal of Heterocyclic Chemistry (1978), 15 (5), 769-72).

  Thus, the result of glyoxyl oxidation by Friedel-Crafts acylation in other cases relevant to the present invention can be a single regioisomer or a mixture of two or more regioisomers. The subject of the present invention is therefore single regioisomers and mixtures of isomers.

（式中、Ｒ_１１およびＲ_１２は互いに独立して、水素、Ｃ_１−Ｃ_１８アルキル、Ｃ_５−Ｃ_１０シクロアルキル、Ｃ_２−Ｃ_１２アルケニル、フェニル−Ｃ_１−Ｃ_４アルキルまたはフェニルであり、
Ｈａｌはハロゲン化物、好ましくは塩化物である）
を用いた、多環式アリール化合物

（式中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７およびＲ_８は、互いに独立して、水素、ハロゲン、Ｃ_１−Ｃ_４アルキル、Ｃ_５−Ｃ_７シクロアルキル、フェニル、Ｃ_１−Ｃ_４アルコキシ、Ｃ_５−Ｃ_７シクロアルコキシ、フェノキシ、Ｃ_１−Ｃ_４−アルキルチオ、Ｃ_５−Ｃ_７シクロアルキルチオ、フェニルチオ、ジ（Ｃ_１−Ｃ_４アルキル）アミノ、ジ（Ｃ_５−Ｃ_７シクロアルキル）アミノ、Ｎ−モルホリニル、Ｎ−ピペリジニルであり、
但し、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７およびＲ_８のうちの少なくとも１つは水素であり、
ＸおよびＹは上記に定義した通りである）
のフリーデル・クラフツアシル化による本発明による式（１）の化合物を調製する方法である。 The invention also relates to novel photoinitiator compounds. The subject of the invention is therefore also the halide compound (2a) or the oxalate compound (4a) or the anhydrous compound (5a) in order to obtain the corresponding glyoxylic acid compound of the formula (1) according to the invention

Wherein R ₁₁ and R ₁₂ are independently of one another hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₂ alkenyl, phenyl-C ₁ -C ₄ alkyl or phenyl. Yes,
Hal is a halide, preferably chloride)
Polycyclic aryl compounds using

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of one another, hydrogen, halogen, C ₁ -C ₄ alkyl, C ₅ -C _7. cycloalkyl, _phenyl, C 1 -C _{4 alkoxy,} C 5 -C ₇ cycloalkoxy, _phenoxy, C 1 -C ₄ - _alkylthio, C 5 -C ₇ cycloalkylthio, phenylthio, di _(C 1 -C ₄ alkyl) amino Di (C ₅ -C ₇ cycloalkyl) amino, N-morpholinyl, N-piperidinyl,
Provided that at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is hydrogen;
X and Y are as defined above)
Is a process for preparing compounds of formula (1) according to the invention by Friedel-Crafts acylation.

（式中、
Ｘは、Ｏ、Ｓまたは直接結合であり、
Ｙは、Ｏ、ＳまたはＣＲ_９Ｒ_１０であり、
Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７およびＲ_８は、互いに独立して、水素、ハロゲン、Ｃ_１−Ｃ_１８アルキル、Ｃ_５−Ｃ_１０シクロアルキル、Ｃ_２−Ｃ_１８アルケニル、フェニル、Ｃ_１−Ｃ_４アルコキシ、Ｃ_５−Ｃ_７シクロアルコキシ、フェノキシ、Ｃ_１−Ｃ_４−アルキルチオ、Ｃ_５−Ｃ_７シクロアルキルチオ、フェニルチオ、ジ（Ｃ_１−Ｃ_４アルキル）アミノ、ジ（Ｃ_５−Ｃ_７シクロアルキル）アミノ、Ｎ−モルホリニル、Ｎ−ピペリジニルまたは式（２）の基

であり、
但し、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７またはＲ_８のうちの１つまたは１つより多くは式（２）の基であり、
Ｒ_９、Ｒ_１０は独立して、水素、Ｃ_１−Ｃ_１８アルキル、Ｃ_２−Ｃ_１２アルケニル、Ｃ_５−Ｃ_１０シクロアルキル、フェニル−Ｃ_１−Ｃ_４アルキル、フェニルであるか、またはそれらが結合するＣ原子と一緒に５員環、６員環もしくは７員環を形成し、
Ｒ_１１は、水素、Ｃ_１−Ｃ_１８アルキル、Ｃ_５−Ｃ_１０シクロアルキル、Ｃ_２−Ｃ_１２アルケニル、フェニル−Ｃ_１−Ｃ_４アルキルまたはフェニルである）
とを含む光重合性組成物に関する。 According to the present invention, the compound of formula (1) can be used as a photoinitiator for the photopolymerization of ethylenically unsaturated compounds. Accordingly, the present invention also provides (A) at least one ethylenically unsaturated photopolymerizable compound and (B) at least one photoinitiator of formula (1).

(Where
X is O, S or a direct bond,
Y is O, S or CR ₉ R ₁₀ ;
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, halogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₈ alkenyl, _phenyl, C 1 -C _{4 alkoxy,} C 5 -C ₇ cycloalkoxy, _phenoxy, C 1 -C ₄ - _alkylthio, C 5 -C ₇ cycloalkylthio, phenylthio, di _(C 1 -C ₄ alkyl) amino, di _(C 5 -C ₇ cycloalkyl) amino, N- morpholinyl, N- piperidinyl, or a group of formula (2)

And
Provided that one or more of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2);
R ₉ and R ₁₀ are independently hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₀ cycloalkyl, phenyl-C ₁ -C ₄ alkyl, phenyl, or Together with the C atom to which
R ₁₁ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₂ alkenyl, phenyl-C ₁ -C ₄ alkyl or phenyl)
And a photopolymerizable composition comprising:

  In addition to component (B), the composition comprises (x) at least one additional photoinitiator (C), and / or (xi) further coinitiators (D), and / or (xii) others The additive (E) may be included.

  The unsaturated compound may contain one or more olefinic double bonds. These may be low molecular weight (monomer) or high molecular weight (oligomer). Examples of monomers containing double bonds are alkyl or hydroxyalkyl acrylates or methacrylates, for example methyl, ethyl, butyl, 2-ethylhexyl or 2-hydroxyethyl acrylate, isobornyl acrylate, methyl methacrylate or ethyl methacrylate. . Also of interest are resins modified with silicon or fluorite, such as silicon acrylate. Other examples are acrylonitrile, acrylamide, methacrylamide, N-substituted (meth) acrylamide, vinyl esters such as vinyl acetate, vinyl ethers such as isobutyl vinyl ether, styrene, alkyl- and halostyrenes, N-vinyl pyrrolidone, vinyl chloride or vinylidene chloride. It is.

  Examples of monomers containing two or more double bonds are ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene glycol or diacrylate of bisphenol A, and 4,4′-bis (2-acryl- Oiloxyethoxy) diphenylpropane, trimethylolpropane triacrylate, pentaerythritol triacrylate or tetraacrylate, vinyl acrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate or tris (2-acryloylethyl) ) Isocyanurate.

  Examples of relatively high molecular weight (oligomer) polyunsaturated compounds are acrylated epoxy resins, acrylated polyesters, vinyl ethers or polyesters containing epoxy groups, and acrylated polyurethanes and polyethers. Further examples of unsaturated oligomers include unsaturated polyester resins, which are usually made from maleic acid, phthalic acid and one or more diols and have a molecular weight of about 500 to 3000. It is also possible to use vinyl ether monomers and oligomers and maleate ester-terminated oligomers having polyester, polyurethane, polyether, polyvinyl ether and epoxy backbones. Particularly suitable are mixtures of oligomers having vinyl ether groups and polymers described in WO 90/01512. However, copolymers of vinyl ether and maleic acid functional monomers are also suitable. This type of unsaturated oligomer is also called a prepolymer.

  Particularly suitable examples are esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers having ethylenically unsaturated groups in the chain or side groups, such as unsaturated polyesters, polyamides and polyurethanes and copolymers thereof, Alkyd resins, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers containing (meth) acrylic groups in the side chain, and mixtures of one or more of these polymers.

  Examples of unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, and unsaturated fatty acids such as linolenic acid and oleic acid. Acrylic acid and methacrylic acid are preferred.

  Suitable polyols are aromatic polyols and in particular aliphatic and cycloaliphatic polyols. Examples of aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di (4-hydroxyphenyl) propane, and novolaks and resoles. Examples of polyepoxides are based on the abovementioned polyols, in particular aromatic polyols and epichlorohydrin. Other preferred polyols are polymers and copolymers containing hydroxyl groups in the polymer chain or side groups, examples being polyvinyl alcohol and copolymers thereof, or polyhydroxyalkyl methacrylates or copolymers thereof. Further polyols that are suitable are oligoesters having hydroxyl end groups.

  Examples of aliphatic and alicyclic polyols are preferably alkylene diols having 2 to 12 carbon atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3. -Or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, preferably polyethylene glycol having a molecular weight of 200 to 1500, 1,3-cyclopentanediol, 1,2- 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris (β-hydroxyethyl) amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sodium It is a Bitoru like.

  Polyols may be partially or fully esterified with one carboxylic acid or various unsaturated carboxylic acids, where some of the esters are modified with free hydroxyl groups, such as etherified with other carboxylic acids or It may be esterified.

Examples of esters are:
Trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate Acrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol diacrylate Tacrylate, pentaerythritol trimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol tetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritol diitaconate, dipentaerythritol trisitaconate, dipentaerythritol pen titaconate, dipentaerythritol hexaitaco Acrylate, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol diitaconate, sorbitol triacrylate, sorbitol tetraacrylate, pentaerythritol modified triacrylate, sorbitol Tetramethacrylate, sorbitol pentaacrylate Sorbitol hexaacrylate, oligoester acrylates and methacrylates, glycerol diacrylate and triacrylate, 1,4-cyclohexane diacrylate, bisacrylates and bismethacrylates of polyethylene glycol having a molecular weight of 200 to 1500, or mixtures thereof.

  Also suitable as component (A) are amides of the same or different unsaturated carboxylic acids and preferably aromatic, cycloaliphatic and aliphatic polyamines having 2-6, especially 2-4 amino groups. . Examples of such polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6 -Hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di-β-aminoethyl ether, diethylenetriamine, triethylenetetramine, di (β-amino Ethoxy)-or di (β-aminopropoxy) ethane. Other suitable polyamines are preferably polymers and copolymers having additional amino groups in the side chain, and oligoamides having amino end groups. Examples of such unsaturated amides are methylene bisacrylamide, 1,6-hexamethylene bisacrylamide, diethylenetriamine trismethacrylamide, bis (methacrylamidepropoxy) ethane, β-methacrylamide ethyl methacrylate and N [(β-hydroxyethoxy ) Ethyl] acrylamide.

  Preferred unsaturated polyesters and polyamides are derived, for example, from maleic acid and from diols or diamines. Some of the maleic acid can be replaced with other dicarboxylic acids. These can be used together with an ethylenically unsaturated comonomer such as styrene. Polyesters and polyamides may be derived from dicarboxylic acids, and may be derived from ethylenically unsaturated diols or diamines, particularly those having relatively long chains, such as those having 6 to 20 carbon atoms. Examples of polyurethanes are those consisting of saturated or unsaturated diisocyanates and, respectively, unsaturated or saturated diols.

  Polybutadiene and polyisoprene and copolymers thereof are known. Examples of suitable comonomers are olefins such as ethylene, propene, butene and hexene, (meth) acrylates, acrylonitrile, styrene or vinyl chloride. Polymers having (meth) acrylate groups in the side chain are likewise known. They may be, for example, reaction products of novolak epoxy resins with (meth) acrylic acid, or homo- or copolymers of vinyl alcohol or its hydroxyalkyl derivatives esterified with (meth) acrylic acid. It may be a homo- and copolymer of (meth) acrylates esterified with hydroxyalkyl (meth) acrylates.

  The photopolymerizable compounds can be used alone or in any desired mixture. It is preferred to use a mixture of polyol (meth) acrylates.

  Binders can also be added to these new compositions, which are particularly suitable when the photopolymerizable compound is a liquid or viscous material. The amount of the binder is, for example, 5% to 95%, preferably 10% to 90%, particularly 40% to 90% by weight based on the total solid amount. The binder is selected according to the field to which it is applied and the properties required in the field, such as developing ability in aqueous or organic solvent systems, adhesion to substrates and sensitivity to oxygen.

  Examples of binders having high molecular weight (oligomer) polyunsaturated compounds are acrylate epoxy resins, acrylate or vinyl-ether- or epoxy group-containing polyesters, polyurethanes and polyethers.

  Examples of suitable binders are polymers having a molecular weight of about 1000 to 2 million, preferably 10,000 to 1000000. Examples are: homo and copolymers of acrylates and methacrylates, such as copolymers of methyl methacrylate / ethyl acrylate / methacrylic acid, poly (alkyl methacrylates), poly (alkyl acrylates); cellulose esters and cellulose ethers, such as cellulose Acetate, cellulose acetobutyrate, methyl cellulose, ethyl cellulose, etc .; polyvinyl butyral, polyvinyl formal, cyclized rubber, polyethers such as polyethylene oxide, polypropylene oxide and polytetrahydrofuran; polystyrene, polycarbonate, polyurethane, chlorinated polyolefin, polyvinyl chloride, vinyl chloride / Vinylidene copolymer, vinylidene chloride and acrylonitrile Polymers, methyl methacrylate and vinyl acetate, polyvinyl acetate, copoly (ethylene / vinyl acetate), polymers such as polycaprolactam and poly (hexamethylene adipamide), and polyesters such as poly (ethylene glycol terephthalate) and poly (hexa succinate) Methylene glycol), and polyimide.

  A suitable binder may be a powder.

  The unsaturated compound can also be used as a mixture with a non-photopolymerizable film-forming component. These may be, for example, physically dried polymers or organic solvent solutions thereof, such as nitrocellulose or cellulose acetobutyrate. However, they may be chemically and / or heat curable (thermosetting) resins, examples being polyisocyanates, polyepoxides and melamine resins, and polyimide precursors. For use in a system known as a hybrid system, it is important to simultaneously use a thermosetting resin, which is photopolymerized in the first stage and crosslinked by post-treatment with heat in the second stage. The binder can simultaneously have radical photopolymerization and chemical or thermosetting functions. It is a so-called dual-cure type binder.

  In addition to the photoinitiator, the photopolymerizable mixture may contain various additives (E). These examples are heat inhibitors, which are intended to prevent immature polymerization, such as hydroquinone, hydroquinine derivatives, p-methoxyphenol, β-naphthol or 2,6-diene. There are sterically hindered phenols such as tert-butyl-p-cresol. In order to improve stability during storage in the dark, for example, copper compounds such as copper naphthenate, copper stearate, copper octoate, etc. and phosphorus compounds such as triphenylphosphine, tributylphosphine, triethylphosphite, triphenyl Phosphites or tribenzyl phosphites, quaternary ammonium compounds such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives such as N-diethylhydroxylamine can be used. Paraffin or similar waxy material can be added to block oxygen from the atmosphere during the polymerization, and these materials that are poorly soluble in the polymer will migrate to the surface at the beginning of the polymerization. Thus, a transparent surface layer that prevents air from entering is formed. It is also possible to apply an oxygen-impermeable layer. Light stabilizers that can be added in small amounts are UV absorbers, for example hydroxyphenylbenzotriazole, hydroxyphenyl-benzophenone, oxamide or hydroxyphenyl-s-triazine type UV absorbers. These compounds can be used individually or as a mixture and can be used with or without sterically hindered amines (HALS).

  Examples of such UV absorbers and light stabilizers are disclosed in WO 04/074328, page 12, line 9 to page 14, line 23, the disclosure of which is hereby incorporated by reference. . Additional known additives may be added, examples being antistatic agents, flow improvers and adhesion promoters.

  To facilitate photopolymerization, amines such as triethanolamine, N-methyldiethanolamine, p-dimethylaminobenzoic acid or Michler's ketone can be added. The action of amines can be enhanced by the addition of benzophenone type aromatic ketones. An example of an amine that can be used as an oxygen scavenger is a substituted N, N-dialkylaniline as described in EP 339841. Other accelerators, coinitiators and autooxides are thiols, thioethers, disulfides, phosphonium salts, phosphines, as described, for example, in European Patent No. 438123, British Patent No. 2180358 and JP-A-6-68309. Oxide or phosphine.

  A chain transfer agent common in the art can be further added to the composition according to the present invention. Examples are mercaptans, amines and benzothiazoles.

  Photopolymerization can also be facilitated by adding additional photosensitizers that shift or extend the spectral sensitivity. These include in particular aromatic carbonyl compounds such as benzophenone, thioxanthone, anthraquinone and 3-acylcoumarin derivatives, 3- (aroylmethylene) thiazoline, camphorquinone, as well as eosin, rhodamine and erythrosine dyes and All compounds that can be used as initiators.

  Examples of suitable sensitizer compounds (D) are described in WO 06/008251, page 36, line 30 to page 38, line 8, which description is incorporated herein by reference.

In some embodiments, the present invention relates to the use of the following compounds as photoinitiators:

  The curing process can be assisted by adding components that form free radicals under thermal conditions. For example, azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), triazenes, diazo sulfides, pentaazadienes and the like, or peroxy compounds such as hydroxy peroxides or peroxy carbonates such as t- Butyl hydroperoxide, which is described, for example, in EP 245639.

  The composition according to the invention can be used as a further additive (E) by photoreducing dyes such as xanthene-, benzoxanthene-, benzothioxanthene, thiazine-, pyronin-, porphyrin- or acridine dyes and / or irradiation. It may have a cleavable trihalogenmethyl compound. Similar compositions are described, for example, in EP 445624. Further common additives are, depending on the intended use, optical brighteners, fillers, pigments, dyes, wetting agents or leveling aids. In order to cure thick colored films, it is preferable to add glass microspheres or powdered glass fibers, as described, for example, in US Pat. No. 5,013,768.

  The present composition may have a dye and / or a white or colored pigment. Depending on the application, organic and inorganic pigments are used. Such additives are known to those skilled in the art and include, for example, titanium dioxide pigments such as rutile or anatase, carbon black Russ, zinc oxide such as zinc white, iron oxide such as iron oxide yellow Iron oxide red, etc., such as chrome yellow, chrome green, nickel titanium yellow, ultramarine blue, cobalt blue, bismuth vanadate, cadmium yellow or cadmium red. Examples of organic pigments are mono or bisazo pigments, as well as their metal complexes, phthalocyanine pigments, polycyclic pigments such as perylene, anthraquinone, thioindigo, quinacridone or triphenylmethane pigments, diketo-pyrrolo-pyrrole, There are isoindolinones such as tetrachloroisoindolinone, isoindoline, dioxazine, benzimidazolone and chinophthalone pigments. The pigments can be used alone or in combination in the composition according to the present invention.

  Depending on the intended use, the pigments can be used in amounts common in the art, for example from 1% to 60% by weight or from 10% to 30% by weight relative to the total formulation.

  The composition may have various organic dyes. Examples are azo dyes, methine dyes, anthraquinone dyes or metal complex dyes. Typical concentrations are for example 0.1% to 20%, in particular 1% to 5%, based on the total formulation.

  The additive is selected according to the field used and the properties required in the field. The above additives are common in the art and are added in the usual amounts for each application.

  In the present invention, a composition containing at least one ethylenically unsaturated photopolymerizable compound emulsified, dispersed or dissolved in water as a component (A) is also provided. Various such radiation curable aqueous prepolymer dispersions are commercially available.

  A prepolymer dispersion is understood to be a dispersion of water and at least one prepolymer dispersed therein. The amount of radiation curable prepolymer or prepolymer mixture dispersed in water ranges, for example, from 20% to 95% by weight, in particular from 30% to 70% by weight. The total percentage of water and prepolymer in this composition is both 100, to which various amounts of auxiliaries and additives (eg emulsifiers) are added depending on the intended use.

  Radiation curable aqueous prepolymer dispersions are known polymer systems and have mono- or polyfunctional ethylenically unsaturated prepolymers with an average molecular weight Mn (g / mol) of at least 400, in particular from 500 to 100,000. . However, depending on the intended use, higher molecular weight prepolymers are also conceivable. What is used is, for example, a polyester with an acid number not exceeding 10, a polyether containing a polymerizable C—C double bond, a polyepoxide containing at least two epoxide groups per molecule and at least one α, Acrylic copolymer containing hydroxyl-containing reaction product with β-ethylenically unsaturated carboxylic acid, polyurethane (meth) acrylate, and α, β-ethylenically unsaturated acrylic radical, described in European Patent No. 12339 . Mixtures of these prepolymers can be used as well. Also suitable are the polymerizable prepolymers described in EP 33896, which have an average molecular weight Mn (g / mol) of at least 600 and further have a polymerizable C—C double bond. It is a thioether adduct of a polymer. Other suitable aqueous dispersions are those of the specific alkyl (meth) acrylate polymer system described in EP 41125.

  Additional additives that can be added to these radiation curable aqueous prepolymer dispersions include dispersion aids, emulsifiers, antioxidants, light stabilizers, dyes, pigments, fillers such as talc, gypsum, silicic acid, rutile, carbon. Black, zinc oxide, iron oxide, reaction accelerators, smoothing agents, lubricants, wetting agents, thickeners, matting agents, antifoaming agents and other auxiliary aids in other coating techniques. Suitable dispersing aids are high molecular weight, water-soluble organic compounds containing polar groups, examples being polyvinyl alcohol, polyvinyl pyrrolidone or cellulose ether. As an emulsifier, a nonionic emulsifier can be used, and an ionic emulsifier can also be used as needed.

（式中、ｓ＝１〜２０）、
下記の２種の化合物の混合物

（式中、ｑ＝約２）、

（式中、ｄおよびｅの合計は約１４であり、ｄはｅより大きい）；

（式中、ｆ＝約１４）、

（式中、ｇ＝約１２）、

（式中、ｈ＝約１３）
および上記化合物のあらゆる配合物または混合物；チオキサントン、チオキサントン誘導体、高分子チオキサントン、例えばＯＭＮＩＰＯＬＴＸ；ケタール化合物、例えばベンジルジメチルケタール；アセトフェノン、アセトフェノン誘導体、例えばα−ヒドロキシシクロアルキルフェニルケトンまたはα−ヒドロキシアルキルフェニルケトン、例えば２−ヒドロキシ−２−メチル−１−フェニル−プロパノン、１−ヒドロキシ−シクロヘキシル−フェニル−ケトン、１−（４−ドデシルベンゾイル）−１−ヒドロキシ−１−メチル−エタン、１−（４−イソプロピルベンゾイル）−１−ヒドロキシ−１−メチル−エタン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパ−１−オン等；２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−ベンジル］−フェニル｝−２−メチル−プロパ−１−オン；２−ヒドロキシ−１−｛４−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−フェノキシ］−フェニル｝−２−メチル−プロパ−１−オン；ジアルコキシアセトフェノン、α−ヒドロキシ−またはα−アミノアセトフェノン、例えば（４−メチルチオベンゾイル）−１−メチル−１−モルフォリノエタン、（４−モルフォリノベンゾイル）−１−ベンジル−１−ジメチルアミノプロパン、（４−モルフォリノベンゾイル）−１−（４−メチルベンジル）−１−ジメチルアミノプロパン、（４−（２−ヒドロキシエチル）アミノベンゾイル）−１−ベンジル−１−ジメチルアミノプロパン）、（３，４−ジメトキシベンゾイル）−１−ベンジル−１−ジメチルアミノプロパン；４−アロイル−１，３−ジオキソラン、ベンゾインアルキルエーテルおよびベンジルケタール、例えばジメチルベンジルケタール、フェニルグリオキサルエステルおよびその誘導体、例えばメチルα−オキソベンゼンアセテート、オキソ−フェニル−酢酸２−（２−ヒドロキシ−エトキシ）−エチルエステル、フェニルグリオキサルエステル二量体、例えばオキソ−フェニル−酢酸１−メチル−２−［２−（２−オキソ−２−フェニル−アセトキシ）−プロポキシ］−エチルエステル；ケトスルホン、例えばＥＳＡＣＵＲＥＫＩＰ１００１Ｍ；オキシムエステル、例えば１，２−オクタンジオン１−［４−（フェニルチオ）フェニル］−２−（Ｏ−ベンゾイルオキシム）、エタノン１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−１−（Ｏ−アセチルオキシム）、９Ｈ−チオキサンテン−２−カルボキシアルデヒド９−オキソ−２−（Ｏ−アセチルオキシム）、過酸エステル、例えば欧州特許第１２６５４１号等に記載のベンゾフェノンテトラカルボン酸過酸エステル、モノアシルホスフィンオキシド、例えば（２，４，６−トリメチルベンゾイル）ジフェニルホスフィンオキシド、エチル（２，４，６トリメチルベンゾイルフェニル）ホスフィン酸エステル；ビスアシルホスフィンオキシド、例えばビス（２，６−ジメトキシ−ベンゾイル）−（２，４，４−トリメチル−ペンチル）ホスフィンオキシド、ビス（２，４，６−トリメチルベンゾイル）−フェニルホスフィンオキシド、ビス（２，４，６−トリメチルベンゾイル）−２，４−ジペントキシフェニルホスフィンオキシド、トリアシルホスフィンオキシド、ハロメチルトリアジン、例えば２−［２−（４−メトキシ−フェニル）−ビニル］−４，６−ビス−トリクロロメチル−［１，３，５］トリアジン、２−（４−メトキシ−フェニル）−４，６−ビス−トリクロロメチル−［１，３，５］トリアジン、２−（３，４−ジメトキシ−フェニル）−４，６−ビス−トリクロロメチル−［１，３，５］トリアジン、２−メチル−４，６−ビス−トリクロロメチル−［１，３，５］トリアジン、ヘキサアリールビスイミダゾール／共開始剤系、例えばオルト−クロロヘキサフェニル−ビスイミダゾールの２−メルカプトベンゾチアゾールとの組み合わせ、フェロセニウム化合物、またはチタノセン、例えばビス（シクロペンタジエニル）−ビス（２，６−ジフルオロ−３−ピリル−フェニル）チタン。また、ホウ酸化合物を共開始剤として用いることができる。さらなる光開始剤として、オリゴマー化合物、例えばα−ヒドロキシルケトンオリゴマー、例えば２−ヒドロキシ−１−｛１−［４−（２−ヒドロキシ−２−メチル−プロピオニル）−フェニル］−１，３，３−トリメチル−インダン−５−イル｝−２−メチル−プロパ−１−オン、ＥＳＡＣＵＲＥＫＩＰ、またはα−アミノケトンオリゴマーを用いることもできる。 In some cases it may be advantageous to use a mixture of two or more novel photoinitiators. Of course, mixtures with known photoinitiators (C) can also be used, for example mixtures with: camphorquinone; benzophenone, benzophenone derivatives, such as 2,4,6-trimethylbenzophenone, 2-methylbenzophenone 3-methylbenzophenone, 4-methylbenzophenone, 2-methoxycarbonylbenzophenone, 4,4′-bis- (chloromethyl) benzophenone, 4-chlorobenzophenone, 4-phenylbenzophenone, 3,3′-dimethyl-4-methoxy -Benzophenone, [4- (4-methylphenylthio) phenyl] -phenylmethanone, methyl-2-benzoylbenzoate, 3-methyl-4'-phenylbenzophenone, 2,4,6-trimethyl-4'-phenylbenzophenone 4,4′-bis (dimethyl) Mino) benzophenone, 4,4'-bis (diethylamino) benzophenone,

(Where s = 1 to 20),
A mixture of the following two compounds

(Where q = about 2),

(Wherein the sum of d and e is about 14 and d is greater than e);

(Where f = about 14),

(Where g = about 12),

(Where h = about 13)
And any blend or mixture of the above compounds; thioxanthone, thioxanthone derivatives, polymeric thioxanthone, such as OMNIPOLTX; ketal compounds, such as benzyldimethyl ketal; acetophenone, acetophenone derivatives, such as α-hydroxycycloalkyl phenyl ketone or α-hydroxyalkylphenyl ketone For example, 2-hydroxy-2-methyl-1-phenyl-propanone, 1-hydroxy-cyclohexyl-phenyl-ketone, 1- (4-dodecylbenzoyl) -1-hydroxy-1-methyl-ethane, 1- (4- Isopropylbenzoyl) -1-hydroxy-1-methyl-ethane, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-prop-1-one, etc .; Droxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-prop-1-one; 2-hydroxy-1- {4- [4- (2-Hydroxy-2-methyl-propionyl) -phenoxy] -phenyl} -2-methyl-prop-1-one; dialkoxyacetophenone, α-hydroxy- or α-aminoacetophenone, such as (4-methylthiobenzoyl)- 1-methyl-1-morpholinoethane, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane, (4-morpholinobenzoyl) -1- (4-methylbenzyl) -1-dimethylaminopropane , (4- (2-hydroxyethyl) aminobenzoyl) -1-benzyl-1-dimethylaminopropane), (3 , 4-dimethoxybenzoyl) -1-benzyl-1-dimethylaminopropane; 4-aroyl-1,3-dioxolane, benzoin alkyl ethers and benzyl ketals such as dimethylbenzyl ketal, phenylglyoxal esters and derivatives thereof such as methyl α -Oxobenzeneacetate, oxo-phenyl-acetic acid 2- (2-hydroxy-ethoxy) -ethyl ester, phenylglyoxal ester dimer, for example oxo-phenyl-acetic acid 1-methyl-2- [2- (2-oxo -2-phenyl-acetoxy) -propoxy] -ethyl ester; ketosulfone, eg ESACUREKIP1001M; oxime ester, eg 1,2-octanedione 1- [4- (phenylthio) phenyl] -2- (O-benzoylo Shim), ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 9H-thioxanthene-2-carboxaldehyde 9-oxo -2- (O-acetyloxime), peracid esters such as benzophenone tetracarboxylic acid peresters described in European Patent 126541, monoacylphosphine oxides such as (2,4,6-trimethylbenzoyl) diphenylphosphine Oxide, ethyl (2,4,6 trimethylbenzoylphenyl) phosphinic acid ester; bisacylphosphine oxide, such as bis (2,6-dimethoxy-benzoyl)-(2,4,4-trimethyl-pentyl) phosphine oxide, bis ( 2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4-dipentoxyphenylphosphine oxide, triacylphosphine oxide, halomethyltriazine, such as 2- [2- (4-methoxy-phenyl) -vinyl ] -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- (4-methoxy-phenyl) -4,6-bis-trichloromethyl- [1,3,5] triazine, 2- (3,4-dimethoxy-phenyl) -4,6-bis-trichloromethyl- [1,3,5] triazine, 2-methyl-4,6-bis-trichloromethyl- [1,3,5] triazine, Hexaarylbisimidazole / co-initiator system, for example, ortho-chlorohexaphenyl-bisimidazole in combination with 2-mercaptobenzothiazole Align, ferrocenium compounds, or titanocenes, such as bis (cyclopentadienyl) - bis (2,6-difluoro-3-pyrryl-phenyl) - titanium. Moreover, a boric acid compound can be used as a coinitiator. As further photoinitiators, oligomeric compounds such as α-hydroxyl ketone oligomers such as 2-hydroxy-1- {1- [4- (2-hydroxy-2-methyl-propionyl) -phenyl] -1,3,3- Trimethyl-indan-5-yl} -2-methyl-prop-1-one, ESACUREKIP, or α-aminoketone oligomers can also be used.

When the novel photoinitiator system is used in a hybrid system, in addition to the novel free radical curing agent, a cationic photoinitiator, for example, a peroxide compound such as benzoyl peroxide (other suitable peroxides are described in U.S. Pat. No. 4,950,581, column 19 lines 17-25, for example, aromatic sulfonium, phosphonium or iodonium salts described in US Pat. No. 4,950,581, column 18, line 60 to column 19, line 10, or cyclopentadienyl. -Alene-iron (II) complex salts such as (η ⁶ -iso-propylbenzene) (η ⁵ -cyclopentadienyl) iron (II) hexafluorophosphate or oxime sulfonate are used. Suitable sulfonium salts are, for example, (registered trademark) Cyracure UVI-6990, (registered trademark) CyracureUVI-6974 (Union Carbide), (registered trademark) Degaure KI85 (Degussa), SP-55, SP-150, SP-170 (Asahi). Electrification), GEUVE1014 (General Electric), SarCat® KI-85 (= triarylsulfonium hexafluorophosphate; Sartomer), SarCat® CD1010 (= mixed triarylsulfonium hexafluoroantimonate; Sartomer); Under the trade name SarCat® CD1011 (= mixed triarylsulfonium hexafluorophosphate; Sartomer) It is possible to hand.

  Suitable iodonium salts include, for example, tricumyl iodonium tetrakis (pentafluorophenyl) borate, 4-[(2-hydroxy-tetradecyloxy) phenyl] phenyliodonium hexafluoroantimonate or hexafluorophosphate (SarCat®). TM) CD1012; Sartomer), tricumyl iodonium hexafluorophosphate, 4-isobutylphenyl-4′-methylphenyl iodonium hexafluorophosphate, 4-octyloxyphenyl-phenyliodonium hexafluorophosphate or hexafluoroantimonate, bis ( Dodecylphenyl) iodonium hexafluoroantimonate or hexafluorophosphate, bis (4-methylphenyl) io Donium hexafluorophosphate, bis (4-methoxyphenyl) iodonium hexafluorophosphate, 4-methylphenyl-4′-ethoxyphenyliodonium hexafluorophosphate, 4-methylphenyl-4′-dodecylphenyliodonium hexafluorophosphate, 4- Methylphenyl-4′-phenoxyphenyl iodonium hexafluorophosphate. Of course, any of the above iodonium salts are also compounds with other anions.

  Suitable examples of oxime sulfonates include α- (octylsulfonyloxyimino) -4-methoxycyanide benzyl, 2-methyl-α- [5- [4-[[methyl-sulfonyl] oxy] imino] -2 (5H ) -Thielinidene] -benzeneacetonitrile, 2-methyl-α- [5- [4-[[(n-propyl) sulfonyl] oxy] imino] -2 (5H) -thienidene] -benzeneacetonitrile, 2-methyl-α -[5- [4-[[(Camphoryl) sulfonyl] oxy] imino] -2 (5H) -thielinidene] -benzeneacetonitrile, 2-methyl-α- [5- [4-[[(4-methylphenyl)] Sulfonyl] oxy] imino] -2 (5H) -thielinidene] -benzeneacetonitrile, 2-methyl-α- [5- [4-[[(n-octyl)] Sulfonyl] oxy] imino] -2 (5H) -thienylidene] -benzeneacetonitrile, 2-methyl-α- [5-[[[[[4-[[(4-methylphenyl) sulfonyl] oxy] phenyl] sulfonyl] oxy ] Imino] -2 (5H) -thienylidene] -benzeneacetonitrile, 1,1 '-[1,3-propanediylbis (oxy-4,1-phenylene)] bis [2,2,2-trifluoro-bis [O- (trifluoromethylsulfonyl) oxime] -ethanone, 1,1 ′-[1,3-propanediylbis (oxy-4,1-phenylene)] bis [2,2,2-trifluoro-bis [ O- (propylsulfonyl) oxime] -ethanone, 1,1 ′-[1,3-propanediylbis (oxy-4,1-phenylene)] bis [2,2,2-tri Fluoro-bis [O-((4-methylphenyl) sulfonyl) oxime] -ethanone, 2- [2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro- 1- (Nonafluorobutylsulfonyloxyimino) -heptyl] -fluorene, 2- [2,2,3,3,4,4,4-heptafluoro-1- (nonafluorobutylsulfonyloxyimino) -butyl]- Fluorene, 2- [2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1- (nonafluorobutylsulfonyloxyimino) -heptyl] -9-thia- Fluorene. This list is not meant to limit the further photoinitiator compounds used in combination with the novel compounds of the present invention.

  The present photopolymerizable composition usually has 0.05 to 15% by weight, preferably 0.1 to 10% by weight of photoinitiator, based on the composition. This amount is the sum of all photoinitiators added when a mixture of photoinitiators is used. This amount is therefore either photoinitiator (B) or photoinitiator (B) + (C).

  The photopolymerizable composition can be used for various purposes, for example, printing, such as intaglio printing, flexographic printing, screen printing, offset printing, gravure printing, lithography, or continuous or droplet ink jet printing. For example, publishing, packaging or transport, delivery, advertising, anti-counterfeiting printing or office supplies for materials pre-treated with generally known formulations according to the method disclosed in WO 03/064061, for example In the field, for example for wood or metal, as a transparent finish, colored finish, white finish, especially for paper, wood, metal or plastic, as a powder coating, as a coating agent, and for buildings and road surfaces As a sunlight-curable coating for signs, for photocopying technology For holographic recording materials, for image recording technology, for the production of printing plates that can be developed with organic solvents or aqueous alkaline solutions, for the production of screen printing masks, as a dental filler composition, as an adhesive, as a pressure sensitive adhesive As an agent, as a laminating resin, as a photoresist, such as an etch resist, an electroplating resist or a permanent resist, etc., either a liquid film or a dry film, as an optical structural dielectric, and as a solder mask for electronic circuits, all kinds For manufacturing optical filters, optical gratings (interference gratings), optical circuits as resists for producing color filters for display applications, or for producing structures in the manufacturing process of plasma display panels and electroluminescent displays For example, as described in U.S. Pat. No. 4,575,330, for the production of three-dimensional products by mass curing (UV curing in a transparent mold) or by stereolithography techniques, composites (for example glass fibers as required) And / or other fibers and styrene polyesters that may contain other auxiliaries) and other thick layer compositions, for coating or sealing electronic components and chips, or as optical fiber coatings, or optical lenses, For example, it can be used for manufacturing contact lenses or Fresnel lenses.

  The composition according to the present invention is further suitable for the production of medical devices, auxiliary devices or implants.

  Furthermore, the composition according to the invention is suitable for the production of gels having thermotropic properties as described, for example, in German Patent No. 19700064 and European Patent No. 678534.

  Compositions according to the present invention are described, for example, in Paint & Coatings Industry, April 1997, 72 or Plastics World, vol. 54, no. 7, p48 (5).

  The novel photoinitiator is further used as an initiator for emulsion polymerization, pearl polymerization or suspension polymerization, as a polymerization initiator for fixing the alignment state of liquid crystal monomers and oligomers, or for fixing dyes to organic materials. It may be used as an initiator.

  In the coating material, a mixture of a prepolymer and a polyunsaturated monomer is often used, and this mixture may further contain a monounsaturated monomer. It is the prepolymer that mainly determines the properties of the coating film, and skilled workers can influence the properties of the cured film by changing this. The polyunsaturated monomer also functions as a cross-linking agent that renders the film insoluble. Monovalent unsaturated monomers act as reactive diluents and are used to reduce viscosity without the use of solvents.

  Unsaturated polyester resins are usually used in two-component systems together with monounsaturated monomers, preferably styrene. For the photoresist, a specific one-component system such as polymaleimide, polychalcone, or polyimide described in German Patent No. 2,308,830 is often used.

  The novel photoinitiators and photoinitiator mixtures can also be used for the polymerization of radiation curable powder coatings. Powder coatings may be based on solid resins and monomers containing double bonds such as maleates, vinyl ethers, acrylates, acrylamides and mixtures thereof. Free radical UV curable powder coatings can be formulated by mixing an unsaturated polyester resin with solid acrylamide (eg methyl methyl acrylamide glycolate) and a new free radical photoinitiator, For example, M.M. Wittig and Th. It is described in the paper “Radiation Curing of Powder Coating” by Gohmann, Conference Processings, Radtech Europe 1993. The powder coating may comprise a binder as described, for example, in DE 4228514 and EP 636669. Free radical UV curable powder coatings can also be formulated by mixing an unsaturated polyester resin with a solid acrylate, methacrylate or vinyl ether and a novel photoinitiator (or photoinitiator mixture). The powder coating may have a binder as described, for example, in DE 4228514 and EP 636669. The UV curable powder coating may further have a white or colored pigment. For example, rutile titanium dioxide can preferably be used at a concentration of up to 50% by weight in order to impart good hiding power to the cured powder coating. As a procedure, usually, a powder is electrostatically or frictionally electrostatically sprayed on a base material such as metal or wood, and the powder is melted by heating to form a smooth film. Then, a medium pressure mercury lamp, a metal halide lamp is formed. Alternatively, the coating is radiation cured by ultraviolet and / or visible light using a xenon lamp. As an advantage over thermosets, radiation curable powder coatings can extend the flow time after melting the powder particles, in particular to ensure that a smooth and high gloss coating is formed. In contrast to thermosetting systems, radiation curable powder coatings can be formulated to melt at lower temperatures without the undesirable effect of reduced service life. For this reason, it is also suitable as a heat sensitive substrate, for example, a coating of wood or plastic.

  In addition to the novel photoinitiator, the powder coating formulation may also contain a UV absorber. As a preferred example, reference is made to the above.

The novel photocurable compositions are suitable, for example, as coating materials for all kinds of substrates: for example, plastics such as wood, textiles, paper, earthenware, glass, polyester, polyethylene terephthalate, polyolefin or cellulose acetate. Especially film-like plastics and also metals such as Al, Cu, Ni, Fe, Zn, Mg or Co and GaAs, Si or SiO ₂ , with a protective layer applied or image-wise exposure As a result, an image is formed.

  The coating of the substrate can be performed by applying a liquid composition, solution or suspension to the substrate. The solvent and concentration are selected based primarily on the type of composition and the coating method. The solvent should be inert, i.e. not chemically react with the components, and should be removable from the coating during drying. Examples of suitable solvents are ketones, ethers and esters such as methyl ethyl ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone, dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2 -Propanol, 1,2-dimethoxyethane, ethyl acetate, n-butyl acetate and ethyl 3-ethoxypropionate.

  The solution can be applied to known coating techniques such as printing, for example intaglio printing, lithography printing, flexographic printing, ink jet printing, screen printing, gravure printing, spin coating, dip coating, knife coating, curtain coating, brushing, spraying, especially static. It is uniformly applied to the substrate by electrospraying and reverse roll coating, or by electrophoretic deposition. It is also possible to coat the photosensitive layer by applying it to a temporary flexible support and then moving the layer by lamination to the final substrate, for example a copper-clad circuit board.

  The coating amount (film thickness) and the substrate state (layer support) are determined by the desired field of use. The film thickness ranges from about 0.01 μm to over 100 μm, for example 20 mm, or 0.02 cm to 10 cm, preferably 0.5 μm to 100 μm.

  The composition according to the invention is used in UV curable adhesives, for example for the production of pressure sensitive adhesives, laminate adhesives, hot melt adhesives, moisture curing adhesives, silane reactive adhesives or silane reactive sealants, etc. And related applications.

  The adhesive may be a hot melt adhesive, or an aqueous or solvent adhesive, a solventless liquid adhesive, or a two-component reactive adhesive. In particular, a pressure sensitive adhesive (PSA), such as a UV curable hot melt pressure sensitive adhesive, is suitable. The adhesive has, for example, at least one rubber component, at least one resin component as a pressure-sensitive adhesive, and at least one oil component at a weight ratio of 30:50:20, for example. Suitable adhesives are natural or synthetic resins. The person skilled in the art knows suitable components and suitable oily components or rubbers.

  The novel photoinitiators also find use as negative resist formulations that are very sensitive to light and can be developed in aqueous alkaline solutions without swelling. This is for electronics (electroplating resist, etch resist, solder resist), for the production of printing plates such as offset printing plates or flexographic printing plates, for the production of relief printing, lithographic printing, rotary gravure, screen printing printing forms It is suitable as a photoresist for the production of relief copies, for example, for the production of Braille text, for the production of size, for chemical milling, or as a micro-resist in the production of integrated circuits. There are various processing conditions for the layer support and the coating substrate that can be used.

  The composition according to the present invention finds its use also in the production of a layered material of one or more layers for monochromatic or multicolor image recording or image reproduction (copying, copying). Furthermore, the material is also suitable for color proofing systems. This technique uses a formulation containing microcapsules, and image generation can be heat treated after radiation curing. Such systems and techniques and their applications are disclosed, for example, in US Pat. No. 5,376,459.

  Substrates used for recording photographic information include, for example, polyester, cellulose acetate or polymer coated paper films; the substrate for offset printing forms is specially treated aluminum and printed circuit The substrate for manufacturing is a copper-clad laminate, and the substrate for manufacturing integrated circuits is a silicon wafer. The layer thickness for photographic materials and offset printing forms is usually from about 0.5 μm to 10 μm, while for printed circuits it is from 1.0 μm to about 100 μm.

  Subsequent to coating the substrate, removal of the solvent (usually by drying) leaves a photoresist coating on the substrate.

  The term “imagewise” exposure includes exposure through a photomask of a predetermined pattern, such as a slide, and laser or light, for example, which produces an image by computer controlled movement over the surface of a coated substrate. Both exposure and electron beam irradiation by computer control are included. It is also possible to use a mask made of liquid crystal capable of generating a digital image in pixel units. Bertsch, J .; Y. Jezequel, J. et al. C. Andre, Journal of Photochemistry and Photobiology A: Chemistry 1997, 107, p. 275-281 and K.K. -P. Offset Printing 1997, 6, p. 34-37.

  After imagewise exposure of the material, it may be advantageous to perform a short heat treatment prior to development. In this case, only the exposed part is thermally cured. The temperature is usually 50 ° C. to 150 ° C., preferably 80 ° C. to 130 ° C .; the heat treatment time is usually between 0.25 minutes and 10 minutes.

  For example, a conjugated polymer such as polyaniline can be converted from a semiconductive state to a conductive state by proton doping. The oxime-sulfonate of the present invention may be used to form a conductive structure (exposed portion) embedded in an insulating material (non-exposed portion) by imagewise irradiation with a composition having such a conjugated polymer. it can. Such materials can be used, for example, as wiring and connections for manufacturing electrical and electronic equipment. The photocurable composition can further be used in a method for producing a printed board or a photoresist, which are described, for example, in German Patent No. 4013358. In such methods, the composition is exposed briefly to visible light having a wavelength of at least 400 nm, without a mask, before, simultaneously with, or after imagewise irradiation. After exposure and heat treatment (if any), the unexposed parts of the photosensitive coating are removed in a known manner with a developer. As already mentioned, the new composition can be developed with an aqueous alkaline solution. Particularly suitable aqueous alkaline developers are aqueous solutions of tetraalkylammonium hydroxide or aqueous solutions of alkali metal silicates, phosphates, hydroxides and carbonates. If necessary, a small amount of wetting agent and / or organic solvent may be added to these solutions. Examples of common organic solvents that can be added in small amounts to the developer are cyclohexanone, 2-ethoxyethanol, toluene, acetone and mixtures of these solvents.

  Photocuring is very important in printing because the ink drying time is a critical factor in the production rate of the graphic and should be on the order of seconds. UV curable inks are very important for screen printing and offset and flexo inks.

  As already mentioned, the novel mixtures are also very suitable for the production of printing plates. In this application, for example, soluble linear polyamides or styrene / butadiene and / or styrene / isoprene rubbers, polyacrylates or polymethylmethacrylates containing carboxyl groups, polyvinyl alcohols or urethane acrylates with photopolymerizable monomers such as acrylamide and / or Alternatively, a mixture of methacrylamide or acrylate and / or methacrylate and a photoinitiator is used. Films and plates of these systems (wet or dry) are exposed with the negative (or positive) of the original printing plate, and then the uncured part is washed away using a suitable solvent or aqueous solution. Another area in which light curing is used is the coating of metals, such as metal plates, tubes, cans or bottle caps, and the light curing of polymer coatings, such as floor or wall PVC-based coverings. Examples of light curing of paper coatings are colorless varnishing of labels, record sleeves and book covers.

  Also of interest is the use of the novel present compounds and photoinitiator systems for the curing of shaped articles composed of composite compositions. The composite compound may be a self-supporting matrix material, such as a glass fiber fabric, or a plant fiber [K. -P. Mieck, T.M. Reusmann's Kunststoff 85 (1995), 366-370], which is impregnated with a photocurable formulation. Molded parts having composite compounds acquire high mechanical stability and resistance when manufactured using the novel compounds. The novel compounds can also be used as photocuring agents in molding, impregnation and coating compositions, which are described, for example, in EP 7086. Examples of such compositions are gel coat resins, which have stringent requirements for curing activity and anti-yellowing, and fiber reinforced molded articles such as planar or longitudinal or transverse wave dispersion panels. Techniques for producing such shaped articles, such as hand layup, spray layup, centrifugal flow or filament winding, are described in, for example, P.I. H. “Glassaverserverkute Kunststoff” by Selen, page 610, Springer Verlag Berlin-Heidelberg-New York 1967. Examples of products that can be produced by these techniques are boats, fiberboard or chipboard panels coated on both sides with glass fiber reinforced plastic, tubes, containers and the like. Further examples of molding, impregnation and coating compositions are glass fiber-containing molded articles (GRP), such as UP resin gel coats such as corrugated sheets and laminated paper. The laminated paper may be urea resin or melamine resin based. Prior to the manufacture of the laminate, a gel coat is created on a support (eg a film). The novel photocurable composition can also be used for resin casting and for embedding articles such as electronic components. Curing is usually performed using a medium pressure mercury lamp, which is conventionally used in UV curing. However, there is also particular interest in lower intensity lamps, such as those of the TL40W / 03 or TL40W / 05 type. The intensity of these lamps roughly corresponds to the intensity of sunlight. Direct sunlight can also be used for curing. A further advantage is that the composite composition can be molded away from the light source in a partially cured plastic state and then fully cured.

  The compositions and compounds according to the invention can be used in the manufacture of holography, waveguides, optical switches, the advantage being the difference in refractive index formed between the irradiated and unirradiated parts.

  The use of the photocurable composition in imaging techniques and in the optical production of information carriers is also important. In such applications, as already described, the layer (wet or dry) applied to the support is imagewise irradiated with UV or visible light, for example through a photomask, and the unexposed part of the layer is exposed to the developer. It is removed by processing by. Application of the photocurable layer to the metal can also be performed by electrophoretic deposition. Since the exposed portion becomes a polymer by crosslinking, it is insoluble and remains on the support. Appropriate coloring produces a visible image. When the support is a metallized layer, after exposure and development, the unexposed metal can be removed by etching or strengthened by electroplating. In this way, electronic circuits and photoresists can be manufactured.

  The present photopolymerizable composition can be further used for the production of functional glass, which is described, for example, in JP-A-10 287450A.

The photocurable composition of the present invention can be further used for curing a charging monomer, for example, an acrylate having an NH ₄ Cl group or the like. Such compositions are used, for example, in the production of polyelectrolytes or copolymers thereof.

  In the present invention, there is provided a photopolymerization method of a monomer, oligomer or polymer compound containing at least one ethylenically unsaturated double bond, wherein the compound contains at least one photoinitiator or photoinitiator mixture as described above. And irradiating the resulting composition with electromagnetic radiation, for example light with a wavelength of 200 nm to 600 nm or with particle radiation, for example electron beams or X-rays; and light as defined above There is also provided the use of an initiator or photoinitiator mixture for the photopolymerization of a monomer, oligomer or polymer compound comprising at least one ethylenically unsaturated double bond.

  The subject of the invention is colored and uncolored paints and varnishes, powder coatings, printing inks such as screen printing inks, offset, flexographic or ink jet printing inks, printing plates, adhesives, sealings, potting parts, dental Composition, foam, molding compound, composite composition, glass fiber cable coating, screen printing stencil, for the production of three-dimensional objects by stereolithography, and as an image recording material, photoresist composition, decolorizing material Further, it is also the above-described manufacturing method of the image recording material using the decoloring material of the image recording material and microcapsules. The photoinitiators according to the invention are particularly suitable for 3D printing.

  The present invention further provides a coated substrate having at least one surface coated with the above composition. In some embodiments, the composition coated on the substrate can be further cured. That is, it can be polymerized or crosslinked.

  The present invention also relates to an article comprising a polymerized or crosslinked composition obtained by curing the polymerizable composition described above. The article according to the present invention can be obtained, for example, in a three-dimensional printing process (3D printing) such as stereolithography.

  Furthermore, the present invention relates to a polymerized or cross-linked composition obtained by curing the polymerizable composition according to the present invention.

  The sensitivity of the new composition to radiation is usually from about 190 nm to the UV range to the infrared range (about 20000 nm, especially 1200 nm), especially 190 nm to 650 nm (depending on the photoinitiator moiety and with any of the sensitizers mentioned above). Varies depending on the combination) and therefore spans a very wide range. Suitable radiation is present, for example, in sunlight or light from artificial light sources. Therefore, a great variety of light sources can be used. Both point light sources and array light sources ("lamp carpet") are suitable. Examples are carbon arc lamps, xenon arc lamps, medium pressure, ultra high pressure, high pressure and low pressure mercury lamps (which may contain metal halide dopes (metal-halogen lamps)), microwave induced metal vapor lamps, excimer lamps, superactinic Fluorescent tubes, fluorescent lamps, argon incandescent lamps, electronic flashlights, photographic bulbs, electron beams and X-rays. The distance between the lamp and the substrate according to the present invention to be exposed varies depending on the intended use and the type and output of the lamp, and may be, for example, 1 cm to 150 cm. As the laser light source, an excimer laser such as a krypton F laser for exposure at 248 nm is also suitable. A visible laser can also be used. In a preferred embodiment, actinic radiation is provided by a light emitting diode (LED) or an organic light emitting diode (OLED), for example a UV light emitting diode (UV-LED). These LEDs allow the radiation source to be turned on and off instantaneously. Also, UV-LEDs typically have a narrow wavelength distribution and can modify the peak wavelength, and efficiently convert electrical energy into UV radiation.

  As described above, depending on the light source used, it is advantageous to use a sensitizer in many cases. As described above, the sensitizer has an absorption spectrum that matches the emission spectrum of the irradiation source as much as possible.

  The following examples illustrate the present invention in more detail and do not limit the scope of the invention to the examples only. Parts and percentages in the following portions of the specification and in the claims are by weight unless otherwise specified.

キサンテン（１５．０３ｇ、０．０８２ｍｏｌ）を６５ｇの１，２−ジクロロエタンに溶解し、氷浴中で冷却した。次いで、塩化アルミニウム（５４．４０ｇ、０．４０８ｍｏｌ）を撹拌下で添加して、褐色溶液を形成した。１時間以内に、２８ｇの１，２−ジクロロエタン中のクロロオキソ酢酸エチル（４８．１０ｇ、０．３５２ｍｏｌ）の溶液を５℃で充填した。得られた混合物を２０℃で２０時間撹拌し、その後、２５４．２ｇの氷、２５４．８ｇの水、５１．６ｇの３２％塩酸および１７０．０ｇの１，２−ジクロロエタンの撹拌混合物中にゆっくりと注いだ。有機層を分離し、５０ｍＬの水で２回洗浄し、Ｎａ_２ＳＯ_４で乾燥し、蒸発させた。残渣を４０ｇの酢酸エチルに溶解し、５０ｍＬの水で２回洗浄し、Ｎａ_２ＳＯ_４で乾燥し、小パッドのシリカゲルで濾過し、蒸発させて、黄色がかった固体として４．２ｇの化合物１を得た。ｍｐ．１０３〜１０９℃。
^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３），δ［ｐｐｍ］：１．４１（ｔ，６Ｈ），４．２０（ｓ，２Ｈ），４．４８（ｑ，４Ｈ），７．２０（ｄ，２Ｈ），７．９４−７．９６（ｍ，４Ｈ）．
^１３Ｃ−ＮＭＲ（７５．５ＭＨｚ，ＣＤＣｌ_３），δ［ｐｐｍ］：１４．１，２７．１４，６２．５，１１７．５，１２０．３，１２８．３，１３１．６，１３４．８，１５５．９，１６３．８，１８４．４．
ＵＶ−Ｖｉｓ（アセトニトリル）：λ_ｍａｘ＝３２２ｎｍ． A) Synthesis Examples Example 1: Ethyl 2- [7- (2-ethoxy-2-oxo-acetyl) -9H-xanthen-2-yl] -2-oxo-acetate (Compound 1)

Xanthene (15.03 g, 0.082 mol) was dissolved in 65 g of 1,2-dichloroethane and cooled in an ice bath. Aluminum chloride (54.40 g, 0.408 mol) was then added with stirring to form a brown solution. Within 1 hour, a solution of ethyl chlorooxoacetate (48.10 g, 0.352 mol) in 28 g of 1,2-dichloroethane was charged at 5 ° C. The resulting mixture was stirred at 20 ° C. for 20 hours, then slowly into a stirred mixture of 254.2 g ice, 254.8 g water, 51.6 g 32% hydrochloric acid and 170.0 g 1,2-dichloroethane. It was poured. The organic layer was separated, washed twice with 50 mL water, dried over Na ₂ SO ₄ and evaporated. The residue was dissolved in 40 g ethyl acetate, washed twice with 50 mL water, dried over Na ₂ SO ₄ , filtered through a small pad of silica gel and evaporated to give 4.2 g of compound 1 as a yellowish solid. Got. mp. 103-109 ° C.
¹ H-NMR (400 MHz, CDCl ₃ ), δ [ppm]: 1.41 (t, 6H), 4.20 (s, 2H), 4.48 (q, 4H), 7.20 (d, 2H) ), 7.94-7.96 (m, 4H).
¹³ C-NMR (75.5 MHz, CDCl ₃ ), δ [ppm]: 14.1, 27.14, 62.5, 117.5, 120.3, 128.3, 131.6, 134.8, 155.9, 163.8, 184.4.
UV-Vis (acetonitrile): λ _max = 322 nm.

９，９−ジメチルキサンテン（４．５０ｇ、２１ｍｍｏｌ）を３７．５ｇの１，２−ジクロロエタンに溶解した。クロロオキソ酢酸エチル（６．１４ｇ、４５ｍｍｏｌ）を室温で添加した。得られた黄色混合物を−５℃に冷却した。次いで、塩化アルミニウム（６．２８ｇ、４７ｍｍｏｌ）を撹拌下で添加して、暗赤色溶液を形成した。２３℃で２０時間撹拌した後、追加の量のクロロオキソ酢酸エチル（０．６４ｇ、４．６ｍｍｏｌ）を添加し、反応を室温で続けた。２時間後のＴＬＣ分析は、９，９−ジメチルキサンテンの完全な変換を示した。次いで、混合物を撹拌しながら１５０ｇの氷にゆっくりと注いだ。５０ｍＬの１，２−ジクロロエタンおよび１５０ｍＬの水を加えた後、有機層を分離し、１５０ｍＬの水で洗浄し、ＭｇＳＯ_４で乾燥させ、蒸発させた。カラムクロマトグラフィー（５５ｇのシリカゲル、溶離液１：５００ｍＬの酢酸エチル、溶離液２：ジクロロメタン）により、０．５ｇの化合物３および２．５ｇの所望の化合物２を得た。
^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３），δ［ｐｐｍ］：１．４６（ｔ，３Ｈ），１．７２（ｓ，６Ｈ），４．４８（ｑ，２Ｈ），７．０８−７．１１（ｍ，１Ｈ），７．１４−７．１８（ｍ，２Ｈ），７．２３−７．２８（ｍ，１Ｈ），７．４５（ｄ，１Ｈ），７．８９（ｄ，１Ｈ），８．２１（ｓ，１Ｈ）． Example 2: Ethyl 2- (9,9-dimethylxanthen-2-yl) -2-oxo-acetate (Compound 2)

9,9-Dimethylxanthene (4.50 g, 21 mmol) was dissolved in 37.5 g of 1,2-dichloroethane. Ethyl chlorooxoacetate (6.14 g, 45 mmol) was added at room temperature. The resulting yellow mixture was cooled to -5 ° C. Aluminum chloride (6.28 g, 47 mmol) was then added with stirring to form a dark red solution. After stirring at 23 ° C. for 20 hours, an additional amount of ethyl chlorooxoacetate (0.64 g, 4.6 mmol) was added and the reaction continued at room temperature. TLC analysis after 2 hours showed complete conversion of 9,9-dimethylxanthene. The mixture was then slowly poured onto 150 g of ice with stirring. After addition of 50 mL 1,2-dichloroethane and 150 mL water, the organic layer was separated, washed with 150 mL water, dried over MgSO ₄ and evaporated. Column chromatography (55 g of silica gel, eluent 1: 500 mL of ethyl acetate, eluent 2: dichloromethane) gave 0.5 g of compound 3 and 2.5 g of the desired compound 2.
¹ H-NMR (400 MHz, CDCl ₃ ), δ [ppm]: 1.46 (t, 3H), 1.72 (s, 6H), 4.48 (q, 2H), 7.08-7.11. (M, 1H), 7.14-7.18 (m, 2H), 7.23-7.28 (m, 1H), 7.45 (d, 1H), 7.89 (d, 1H), 8.21 (s, 1H).

化合物２（２．４５ｇ、８ｍｍｏｌ）を３２．３ｇの１，２−ジクロロエタンおよび１ｇのスルホランに溶解した。４．１３ｇの１，２−ジクロロエタンに溶解したクロロオキソ酢酸エチル（４．３８ｇ、ｍｍｏｌ）の溶液を室温で添加した。得られた緑がかった混合物を−３℃に冷却した。次いで塩化アルミニウム（２．３８ｇ、１８ｍｍｏｌ）を撹拌下で添加して、暗赤色混合物を形成した。２３℃で２０時間撹拌した後、追加の量の塩化アルミニウム（４．００ｇ、３０ｍｍｏｌ）を添加し、反応混合物を室温で３０時間撹拌した。次いで、混合物を撹拌しながら１５０ｇの氷にゆっくりと注いだ。３０ｍＬの１，２−ジクロロエタンおよび９０ｍＬの３２％塩酸を加えた後、有機層を分離し、１００ｍＬのブラインで２回洗浄し、ＭｇＳＯ_４で乾燥させ、蒸発させた。カラムクロマトグラフィー（３０ｇのシリカゲル、溶離液：シクロヘキサン／酢酸エチル ９．５：０．５）により、１．０ｇの標題化合物を黄色がかった固体として得た。
^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３），δ［ｐｐｍ］：１．４６（ｔ，６Ｈ），１．７２（ｓ，６Ｈ），４．４９（ｑ，４Ｈ），７．２０（ｄ，２Ｈ），７．９４（ｄｄ，２Ｈ），８．２２（ｄ，２Ｈ）．
^１３Ｃ−ＮＭＲ（７５．５ＭＨｚ，ＣＤＣｌ_３），δ［ｐｐｍ］：１４．１，３２．９，３４．２，６２．４，１１７．４，１２８．８，１２９．５，１３０．３，１３０．７，１５４．３，１６３．７，１８４．６．
ＵＶ−Ｖｉｓ（ＭｅＯＨ）：λ_ｍａｘ＝３１９ｎｍ． Example 3: Ethyl 2- [7- (2-ethoxy-2-oxo-acetyl) -9,9-dimethyl-xanthen-2-yl] -2-oxo-acetate (compound 3)

Compound 2 (2.45 g, 8 mmol) was dissolved in 32.3 g 1,2-dichloroethane and 1 g sulfolane. A solution of ethyl chlorooxoacetate (4.38 g, mmol) dissolved in 4.13 g of 1,2-dichloroethane was added at room temperature. The resulting greenish mixture was cooled to -3 ° C. Aluminum chloride (2.38 g, 18 mmol) was then added with stirring to form a dark red mixture. After stirring at 23 ° C. for 20 hours, an additional amount of aluminum chloride (4.00 g, 30 mmol) was added and the reaction mixture was stirred at room temperature for 30 hours. The mixture was then slowly poured onto 150 g of ice with stirring. After addition of 30 mL 1,2-dichloroethane and 90 mL 32% hydrochloric acid, the organic layer was separated, washed twice with 100 mL brine, dried over MgSO ₄ and evaporated. Column chromatography (30 g of silica gel, eluent: cyclohexane / ethyl acetate 9.5: 0.5) gave 1.0 g of the title compound as a yellowish solid.
¹ H-NMR (400 MHz, CDCl ₃ ), δ [ppm]: 1.46 (t, 6H), 1.72 (s, 6H), 4.49 (q, 4H), 7.20 (d, 2H) ), 7.94 (dd, 2H), 8.22 (d, 2H).
¹³ C-NMR (75.5 MHz, CDCl ₃ ), δ [ppm]: 14.1, 32.9, 34.2, 62.4, 117.4, 128.8, 129.5, 130.3, 130.7, 154.3, 163.7, 184.6.
UV-Vis (MeOH): λ _max = 319 nm.

化合物４は、化合物２と同様にチアントレンから６８％の収率で調製した。
^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３），δ［ｐｐｍ］：１．４４（ｔ，３Ｈ），４．４７（ｑ，２Ｈ），７．２５−７．２９（ｍ，２Ｈ），７．４４−７．５０（ｍ，２Ｈ），７．５７（ｄ，１Ｈ），７．８９（ｄ，１Ｈ），８．１１（ｓ，１Ｈ）． Example 4: Ethyl 2-oxo-2-thianthren-2-yl-acetate (compound 4)

Compound 4 was prepared in 68% yield from thianthrene in the same manner as Compound 2.
¹ H-NMR (400 MHz, CDCl ₃ ), δ [ppm]: 1.44 (t, 3H), 4.47 (q, 2H), 7.25-7.29 (m, 2H), 7.44 -7.50 (m, 2H), 7.57 (d, 1H), 7.89 (d, 1H), 8.11 (s, 1H).

黄色固体の形態の０．１ｇの化合物５をカラムクロマトグラフィーの間に副生成物として単離した、ｍｐ＝１２３〜１２９℃。
ＵＶ−Ｖｉｓ（酢酸エチル）：λ_ｍａｘ＝２８８ｎｍおよび３２７ｎｍ．
^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３），δ［ｐｐｍ］：１．４５（ｔ，６Ｈ），４．４７（ｑ，４Ｈ），７．６０（ｄ，２Ｈ），７．９５（ｄ，２Ｈ），８．１１（ｓ，２Ｈ）． (Compound 5)

0.1 g of compound 5 in the form of a yellow solid was isolated as a by-product during column chromatography, mp = 123-129 ° C.
UV-Vis (ethyl acetate): λ _max = 288 nm and 327 nm.
¹ H-NMR (400 MHz, CDCl ₃ ), δ [ppm]: 1.45 (t, 6H), 4.47 (q, 4H), 7.60 (d, 2H), 7.95 (d, 2H) ), 8.11 (s, 2H).

Example 5: Ethyl 2- [8- (2-ethoxy-2-oxo-acetyl) thianthren-2-yl] -2-oxo-acetate (Compound 5)

Aluminum chloride (37.00 g, 277 mmol) was added in portions to a mixture of ethyl chlorooxoacetate (34.70 g, 254 mmol) and sulfolane (0.60 g) in 100 g of 1,2-dichloroethane. A solution of thianthrene (10.00 g, 46 mmol) in 120 g of 1,2-dichloroethane was added to the red-orange mixture within 1 hour and stirred at room temperature. TLC analysis showed complete conversion of thianthrene after 1 hour. The reaction mixture was poured into water / ice with stirring. The organic layer was separated, washed 3 times with water and evaporated. The crude product was obtained after column chromatography (silica gel, eluent: cyclohexane / ethyl acetate 9: 1). A second column chromatography (silica gel, eluent: toluene / cyclohexane 1: 1) was performed to isolate 0.40 g of the desired compound 5 as a yellowish solid, mp = 123-129 ° C.
UV-Vis (ethyl acetate): λ _max = 288 nm and 327 nm.
¹ H-NMR (400 MHz, CDCl ₃ ), δ [ppm]: 1.45 (t, 6H), 4.47 (q, 4H), 7.60 (d, 2H), 7.95 (d, 2H) ), 8.11 (s, 2H).

Example 6: Ethyl 2- [8- (2-ethoxy-2-oxo-acetyl) dibenzo-p-dioxin-2-yl] -2-oxo-acetate and / or ethyl 2- [7- (2-ethoxy -2-oxo-acetyl) dibenzo-p-dioxin-2-yl] -2-oxo-acetate (compound 6)

  Ethyl chlorooxoacetate (74.7 g, mol) and 0.6 g sulfolane were dissolved in 100 g 1,2-dichloroethane. Aluminum chloride (37.0 g, mol) was carefully added in small portions to give a red-orange mixture. A solution of dibenzodioxin (5.0 g, 0.03 mol) in 120 g of 1,2-dichloroethane was added within 1 hour. The resulting blue-violet mixture was stirred at 25 ° C. for 1.5 hours and then poured into a stirred mixture of 150 g of ice, 100 g of water and 50 g of 32% hydrochloric acid.

The organic layer was separated, washed 3 times with water and dried over Na ₂ SO ₄ . Evaporation of the solvent under vacuum yielded 11.4 g of crude product, which still contained residual sulfolane. The crude product was taken up in 1,2-dichloroacetic acid and washed twice with water (150 g and 80 g) to remove the residual amount of sulfolane. The organic phase was dried over Na ₂ SO ₄ and evaporated. The residue (11 g) was purified by column chromatography (100 g of silica gel, eluent: cyclohexane: ethyl acetate 4: 1) to give 6.0 g of compound 6 as yellowish crystals, mp 133-138 ° C.
¹ H-NMR (400 MHz, CDCl ₃ ), δ [ppm]: 1.44 (t, 6H), 4.46 (q, 4H), 6.99 (dd, 2H), 7.62 (s, 2H) ), 7.71 (d, 2H).
¹³ C-NMR (75.5 MHz, CDCl ₃ ), δ [ppm]: 14.1, 62.5, 116.9, 118.1, 128.1, 129.1, 141.4, 146.9, 163.1, 183.6.
UV-Vis (ethyl acetate): λ _max = 288 nm, 326 nm.

化合物７は、化合物１と同様にフェノトリアジンから２．３％の収率で調製した。赤褐色の強粘性油。
^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３），δ［ｐｐｍ］：１．４５（ｔ，６Ｈ），４．６７（ｑ，４Ｈ），７．１１（ｄ，２Ｈ），８．１０−８．１５（ｍ，４Ｈ）． Example 7: Ethyl 2- [8- (2-ethoxy-2-oxo-acetyl) phenoxathin-2-yl] -2-oxo-acetate (Compound 7)

Compound 7 was prepared in 2.3% yield from phenotriazine in the same manner as Compound 1. Reddish brown viscous oil.
¹ H-NMR (400 MHz, CDCl ₃ ), δ [ppm]: 1.45 (t, 6H), 4.67 (q, 4H), 7.11 (d, 2H), 8.10-8.15 (M, 4H).

化合物８は、化合物１と同様にジベンゾフランから調製した。無色の固体。
^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３），δ［ｐｐｍ］：１．５０（ｔ，６Ｈ），４．５４（ｑ，４Ｈ），７．７６（ｄ，２Ｈ），８．３０（ｄ，２Ｈ），８．７９（ｓ，２Ｈ）．
ＵＶ−Ｖｉｓ（酢酸エチル）：λ_ｍａｘ＝２５７ｎｍおよび２８７ｎｍ． Example 8: Ethyl 2-oxo-2- [8- (2-oxopentanoyl) dibenzofuran-2-yl] acetate (Compound 8)

Compound 8 was prepared from dibenzofuran in the same manner as Compound 1. Colorless solid.
¹ H-NMR (400 MHz, CDCl ₃ ), δ [ppm]: 1.50 (t, 6H), 4.54 (q, 4H), 7.76 (d, 2H), 8.30 (d, 2H) ), 8.79 (s, 2H).
UV-Vis (ethyl acetate): λ _max = 257 nm and 287 nm.

ジメチルフルオレン（４．９３ｇ、２６ｍｍｏｌ）および塩化アルミニウム（２１．００ｇ、１５４ｍｍｏｌ）を、２００ｇの１，２−ジクロロエタンおよび０．３４ｇのスルホラン中で混合した。クロロオキソ酢酸エチル（１９．３６ｇ、１４２ｍｍｏｌ）を撹拌しながら添加した。得られた黒色反応混合物を室温で撹拌した。２．５時間後のＴＬＣ分析は、ジメチルフルオレンの完全な変換を示した。その後、反応混合物を３００ｇの氷／水の撹拌混合物中にゆっくりと注いだ。５０ｍＬの１，２−ジクロロエタンおよび１Ｌの水を加えた後、有機層を分離し、ＭｇＳＯ_４で乾燥し、蒸発させた。残渣（９．２７ｇ）をカラムクロマトグラフィー（１２０ｇのシリカゲル、溶離液１：トルエン／シクロヘキサン ７：３、溶離液２：トルエン／酢酸エチル ９．５：１．５）により精製し、粗生成物４．５ｇを得た。カラムクロマトグラフィー（シリカゲル６５ｇ、溶離液１：トルエン、溶離液２：トルエン／酢酸エチル ９：１）による別の精製を行い、４．６３ｇの化合物９を暗黄色の非常に粘稠な油状物として得た。
^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３），δ［ｐｐｍ］：１．４６（ｔ，６Ｈ），１．６１（ｓ，６Ｈ），４．５１（ｑ，４Ｈ），７．９３（ｄ，２Ｈ），８．０５（ｄ，２Ｈ），８．１７（ｓ，２Ｈ）．
ＵＶ−Ｖｉｓ（アセトニトリル）：λ_ｍａｘ＝３３３ｎｍ． Example 9: Ethyl 2- [9,9-dimethyl-7- (2-oxopentanoyl) fluoren-2-yl] -2-oxo-acetate (Compound 9)

Dimethylfluorene (4.93 g, 26 mmol) and aluminum chloride (21.00 g, 154 mmol) were mixed in 200 g 1,2-dichloroethane and 0.34 g sulfolane. Ethyl chlorooxoacetate (19.36 g, 142 mmol) was added with stirring. The resulting black reaction mixture was stirred at room temperature. TLC analysis after 2.5 hours showed complete conversion of dimethylfluorene. The reaction mixture was then slowly poured into a stirred mixture of 300 g ice / water. After addition of 50 mL 1,2-dichloroethane and 1 L water, the organic layer was separated, dried over MgSO ₄ and evaporated. The residue (9.27 g) was purified by column chromatography (120 g of silica gel, eluent 1: toluene / cyclohexane 7: 3, eluent 2: toluene / ethyl acetate 9.5: 1.5) to give crude product 4 .5 g was obtained. Further purification by column chromatography (silica gel 65 g, eluent 1: toluene, eluent 2: toluene / ethyl acetate 9: 1), 4.63 g of compound 9 as a dark yellow, very viscous oil Obtained.
¹ H-NMR (400 MHz, CDCl ₃ ), δ [ppm]: 1.46 (t, 6H), 1.61 (s, 6H), 4.51 (q, 4H), 7.93 (d, 2H) ), 8.05 (d, 2H), 8.17 (s, 2H).
UV-Vis (acetonitrile): λ _max = 333 nm.

フルオレン（１５．００ｇ、９０ｍｍｏｌ）およびスルホラン（１．１６ｇ）を１００ｍＬの１，２−ジクロロエタンに混合した。塩化アルミニウム（４２．２０ｇ、３１６ｍｍｏｌ）を撹拌しながらゆっくりと添加した。得られた混合物を０℃に冷却した。クロロオキソ酢酸エチル（３７．００ｇ、２７１ｍｍｏｌ）を９０分以内に添加した。得られた赤色の反応混合物を室温で２４時間撹拌した。その後、反応混合物を氷上にゆっくりと注ぎ、室温まで一晩ゆっくりと加温した。有機層を分離し、水で３回洗浄し、蒸発させた。残渣（９．２７ｇ）をフラッシュクロマトグラフィー（シリカゲル、溶離液：ヘキサン／酢酸エチル ４：１）により精製して、２．７ｇの標題化合物を黄色がかった固体として得た。
^１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ_３），δ［ｐｐｍ］：１．４６（ｔ，６Ｈ），４．５０（ｑ，４Ｈ），７．８３（ｄ，２Ｈ），８．００（ｄ，２Ｈ），８．１４（ｓ，２Ｈ）．
ＵＶ−Ｖｉｓ（アセトニトリル）：λ_ｍａｘ＝３３５ｎｍ． Example 10: Ethyl 2-oxo-2- [7- (2-oxopentanoyl) -9H-fluoren-2-yl] acetate (Compound 10)

Fluorene (15.00 g, 90 mmol) and sulfolane (1.16 g) were mixed in 100 mL 1,2-dichloroethane. Aluminum chloride (42.20 g, 316 mmol) was added slowly with stirring. The resulting mixture was cooled to 0 ° C. Ethyl chlorooxoacetate (37.00 g, 271 mmol) was added within 90 minutes. The resulting red reaction mixture was stirred at room temperature for 24 hours. The reaction mixture was then slowly poured onto ice and allowed to warm slowly to room temperature overnight. The organic layer was separated, washed 3 times with water and evaporated. The residue (9.27 g) was purified by flash chromatography (silica gel, eluent: hexane / ethyl acetate 4: 1) to give 2.7 g of the title compound as a yellowish solid.
¹ H-NMR (400 MHz, CDCl ₃ ), δ [ppm]: 1.46 (t, 6H), 4.50 (q, 4H), 7.83 (d, 2H), 8.00 (d, 2H) ), 8.14 (s, 2H).
UV-Vis (acetonitrile): λ _max = 335 nm.

クロロオキソ酢酸エチル（３７．２ｇ、２７０ｍｍｏｌ）および１．１０ｇのスルホランを１，２−ジクロロエタン２００ｍＬに混合した。塩化アルミニウム（４２．１０ｇ、３１６ｍｍｏｌ）を５℃で少しずつゆっくりと添加した。８０ｍＬの１，２−ジクロロエタン中のフルオレン（１５．０ｇ、９０ｍｍｏｌ）の溶液を注意深く添加した。得られた赤色混合物を２５℃で４．５時間撹拌し、次いで１００ｇの氷、１５０ｇの水および５０ｇの３２％塩酸の撹拌混合物に注いだ。 Example 11: Ethyl 2- (9H-fluoren-2-yl) -2-oxo-acetate (Compound 11)

Ethyl chlorooxoacetate (37.2 g, 270 mmol) and 1.10 g of sulfolane were mixed in 200 mL of 1,2-dichloroethane. Aluminum chloride (42.10 g, 316 mmol) was added slowly in portions at 5 ° C. A solution of fluorene (15.0 g, 90 mmol) in 80 mL 1,2-dichloroethane was carefully added. The resulting red mixture was stirred at 25 ° C. for 4.5 hours and then poured into a stirred mixture of 100 g of ice, 150 g of water and 50 g of 32% hydrochloric acid.

The organic layer was separated, washed twice with water and dried over Na ₂ SO ₄ . The solvent was evaporated under vacuum. The residue (28.6 g) was purified by column chromatography (silica gel, heptane: ethyl acetate 9: 1) to give 18.4 g of crude product. The crude product was further purified by column chromatography (silica gel, heptane / toluene 7: 3) to give 15 g of compound 11 as an off-white solid.
¹ H-NMR (400 MHz, CDCl ₃ ), δ [ppm]: 1.48 (t, 3H), 3.98 (s, 2H), 4.51 (q, 2H), 7.38-7.50 (M, 2H), 7.62 (d, 1H), 7.88 (d, 2H), 8.07 (d, 1H), 8.20 (s, 1H).
¹³ C-NMR (75.5 MHz, CDCl ₃ ), δ [ppm]: 14.2, 37.0, 62.3, 120.0, 121.3, 125.4, 126.6, 127.2 / 128.7, 129.7, 130.8, 143.5, 144.7, 148.4, 164.3, 186.3.
UV-Vis (acetonitrile): λ _max = 324 nm.

クロロオキソ酢酸エチル（２４．４ｇ、２７０ｍｍｏｌ）および１．０ｇのスルホランを２００ｍＬの１，２−ジクロロエタンに混合した。塩化アルミニウム（２７．８ｇ、３１６ｍｍｏｌ）を０℃で徐々に少しずつ添加した。５０ｍＬの１，２−ジクロロエタン中のジベンゾフラン（１０．０ｇ、９０ｍｍｏｌ）の溶液を注意深く添加した。得られた赤色混合物を５℃で１時間撹拌し、次いで１５０ｇの氷、１００ｇの水および５０ｇの３２％塩酸の撹拌混合物に注いだ。 Example 12: Ethyl 2-dibenzofuran-2-yl-2-oxo-acetate (Compound 12)

Ethyl chlorooxoacetate (24.4 g, 270 mmol) and 1.0 g sulfolane were mixed into 200 mL 1,2-dichloroethane. Aluminum chloride (27.8 g, 316 mmol) was added slowly at 0 ° C. A solution of dibenzofuran (10.0 g, 90 mmol) in 50 mL of 1,2-dichloroethane was carefully added. The resulting red mixture was stirred at 5 ° C. for 1 hour and then poured into a stirred mixture of 150 g of ice, 100 g of water and 50 g of 32% hydrochloric acid.

The organic layer was separated and washed twice with water and once with brine. The solvent was evaporated under vacuum. The residue was dissolved in ethyl acetate and the resulting organic phase was washed twice with water and once with brine. The solvent was evaporated under vacuum. The residue (13.5 g) was purified twice by column chromatography (column 1: silica gel, heptane: ethyl acetate 9: 1; column 2: silica gel, heptane: toluene 7: 3) to give 3.9 g of the title compound. Obtained as an off-white solid.
¹ H-NMR (400 MHz, CDCl ₃ ), δ [ppm]: 1.49 (t, 3H), 4.54 (q, 2H), 7.40-7.45 (m, 1H), 7.52 -7.56 (m, 1H), 7.60-7.65 (m, 2H), 8.02 (d, 2H), 8.18 (d, 1H), 8.68 (s, 1H).
UV-Vis (acetonitrile): λ _max = 260 nm, 276 nm, 312 nm (shoulder).

B) Application examples Materials-Photoinitiator Irgacure (R) 819 from BASF SE
-Photoinitiator Irgacure (R) TPO from BASF SE
-Photoinitiator Irgacure (R) TPO-L from BASF SE
-Photoinitiator SpeedCure (R) CPTX from Lambson Ltd
-Polymeric amine-modified polyether acrylate Laromar® PO9139 from BASF SE
-Trifunctional monomer acrylate Laromer® LR8863 from BASF SE
-Substrate Melinex (R) 506 transparent polyester film with a thickness of 175 [mu] m from DuPont Teijin Films-spiral bar coater from BYK-Gardner GmbH to achieve a theoretical wet film thickness of 6 [mu] m

Equipment - 365 nm emission wavelength and 12W / cm ² irradiance - IST METZ GmbH steel conveyor belt drive UV having a FirePower FP300 UV LED made Phoseon with (gap UV LED substrate surface was always adjusted to 10 mm) Dryer-Conveyor belt driven UV dryer made by IST METZ GmbH with medium pressure mercury lamp M-300-U2H made by IST METZ GmbH with an electric input of 200 W / cm-Dr. Colorimeter LICO200 made by Bruno Lange
-I.D. from Research Equipment Ltd. C. I. Cone plate viscometer

Test Method—Reactivity was determined as the conveyor belt speed of the UV dryer. Immediately after UV curing in air, the film could no longer be damaged by scratching with fingernails.
-MEK (methyl ethyl ketone) resistance was determined for the film after 24 hours of UV curing as the number of double rubs on a cotton pad soaked with MEK that did not cause visible damage to the film surface-Viscosity was 23 Measured at 0.0 ° C. and a shear rate of 10,000 sec ^−1- APHA color was evaluated by colorimetric analysis

Test formulation

Characteristics of the test formulation

UV reactivity and MEK resistance of test formulations

  The inventive photoinitiators of Example 11 and Example 3 have so far been the only two commercially available photoinitiator classes that impart surface cure under UV LED irradiation, thioxanthone and 4,4′-bis ( Together with the dialkylamino) benzophenone derivative, promotes proper surface curing under UV LED irradiation. In contrast, acylphosphine oxide photoinitiators known to provide through curing under UV LED irradiation are the same even when the corresponding printing is passed several times under UV LED irradiation source. Does not show any surface hardening under the conditions. These results were confirmed by the MEK resistance test, where the photoinitiator of the present invention resulted in excellent solvent resistance for UV curable printing parallel to that of thioxanthone and 4,4′-bis (dialkylamino) benzophenone. .

  The photoinitiators of the invention of Example 11 and Example 3 not only promote proper surface curing under monochromatic UV LED irradiation, but are also very reactive under a multicolor medium pressure mercury lamp. This also leads to the excellent solvent resistance of UV curable printing.

Application Examples in Photopolymers for 3D Printing In the acrylate-based photopolymer for 3D printing, eg stereolithography, comprising the photoinitiator of the invention of Example 11 consisting of two urethane acrylates and one monofunctional monomer At 1.5% by weight. As shown in FIG. 1, the polymerization heat and glass transition temperature of the obtained polymer were determined by photoDSC and DSC (TGA / DSC1, Mettler Toledo) after irradiating a 365 nm LED (40 mW).

Test pieces (thickness 2 mm) for determining the mechanical properties (tensile test, DIN ISO 527-1, test type 5A, Zwick tensile test apparatus, speed 50 mm / min) of the cured polymer are made in-house in a two-stage curing process. Prepared using a silicon mold: Fixing under UVA fluorescent tube (60 seconds, Sylvania Blacklight 368, F40W, T12, distance to sample 11 cm), curing under 2.385 nm LED (double-sided curing, total UV dose 2500 mJ / cm ² ). The determined values are shown in the following table.

Claims (17)

Formula (1)

(Where
X is O, S or a direct bond,
Y is O, S or CR ₉ R ₁₀ ;
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, halogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₈ alkenyl, _phenyl, C 1 -C _{4 alkoxy,} C 5 -C ₇ cycloalkoxy, _phenoxy, C 1 -C ₄ - _alkylthio, C 5 -C ₇ cycloalkylthio, phenylthio, di _(C 1 -C ₄ alkyl) amino, di _(C 5 -C ₇ cycloalkyl) amino, N- morpholinyl, N- piperidinyl, or a group of formula (2)

Provided that one or more of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2);
R ₉ and R ₁₀ are independently of each other hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₀ cycloalkyl, phenyl-C ₁ -C ₄ alkyl, phenyl, or Together with the C atom to which they are attached form a 5-, 6- or 7-membered ring,
R ₁₁ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₂ alkenyl, phenyl-C ₁ -C ₄ alkyl or phenyl;
However,

Are excluded)
Photoinitiator compounds. Compound of formula (3)

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ are as defined in claim 1.
The photoinitiator compound of claim 1, wherein (I) _one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2), or (ii) R ₁ , R ₂ , One of R ₃ or R ₄ is a group of formula (2), and one of R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2);
R ₉ , R ₁₀ and R ₁₁ are as defined in claim 1;
Preferably, R ₉ , R ₁₀ are independently hydrogen, C ₁ -C ₁₈ alkyl, or together with the C atom to which they are attached form a 5-, 6-, or 7-membered ring;
R ₁₁ is C ₁ -C ₁₈ alkyl;
More preferably, R ₉ and R ₁₀ are independently hydrogen or methyl,
R ₁₁ is methyl or ethyl.
The photoinitiator compound according to claim 1 or 2. R _{1 to} R ₄ and R _{5 to} R ₈ different from the group of formula (2) are independently of each other hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio. N-morpholinyl or N-piperidinyl, preferably wherein R _{1 to} R ₄ and R _{5 to} R ₈ different from the group of formula (2) are hydrogen. The photoinitiator compound described. (A) at least one ethylenically unsaturated photopolymerizable compound;
(B) Formula (1)

(Where
X is O, S or a direct bond,
Y is O, S or CR ₉ R ₁₀ ;
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, halogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₈ alkenyl, _phenyl, C 1 -C _{4 alkoxy,} C 5 -C ₇ cycloalkoxy, _phenoxy, C 1 -C ₄ - _alkylthio, C 5 -C ₇ cycloalkylthio, phenylthio, di _(C 1 -C ₄ alkyl) amino, di _(C 5 -C ₇ cycloalkyl) amino, N- morpholinyl, N- piperidinyl, or a group of formula (2)

Provided that one or more of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2);
R ₉ and R ₁₀ are independently of each other hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₀ cycloalkyl, phenyl-C ₁ -C ₄ alkyl, phenyl, or Together with the C atom to which they are attached form a 5-, 6- or 7-membered ring,
R ₁₁ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₂ alkenyl, phenyl-C ₁ -C ₄ alkyl or phenyl)
A photopolymerizable composition comprising at least one photoinitiator compound.   6. The photopolymerizable composition according to claim 5, wherein the at least one photoinitiator of formula (1) is as defined in any one of claims 2-4. In addition to component (B)
(X) at least one further photoinitiator (C),
(Xi) at least one additional coinitiator (D),
(Xii) at least one other additive (E), or (xii) a combination of (x) and (xi) or a combination of (x) and (xii) or (x) and (xi) and (xii) The photopolymerizable composition according to claim 5 or 6, comprising a combination.   8. The photoinitiator compound of formula (1) according to any one of claims 5 to 7, comprising 0.05 to 15% by weight, preferably 0.1 to 10% by weight, based on the total composition. Photopolymerizable composition. A method for the photopolymerization of a monomer, oligomer or polymer compound comprising at least one ethylenically unsaturated double bond, said monomer, oligomer or polymer compound comprising at least one photoinitiator of formula (1)

(Where
X is O, S or a direct bond,
Y is O, S or CR ₉ R ₁₀ ;
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, halogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₈ alkenyl, _phenyl, C 1 -C _{4 alkoxy,} C 5 -C ₇ cycloalkoxy, _phenoxy, C 1 -C ₄ - _alkylthio, C 5 -C ₇ cycloalkylthio, phenylthio, di _(C 1 -C ₄ alkyl) amino, di _(C 5 -C ₇ cycloalkyl) amino, N- morpholinyl, N- piperidinyl, or a group of formula (2)

Provided that one or more of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2);
R ₉ and R ₁₀ are independently hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₀ cycloalkyl, phenyl-C ₁ -C ₄ alkyl, phenyl, or Forms a 5-membered ring, 6-membered ring or 7-membered ring with the C atom to which
R ₁₁ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₂ alkenyl, phenyl-C ₁ -C ₄ alkyl or phenyl)
A step of adding
Irradiating the resulting composition with electromagnetic radiation or specific radiation.   10. A method according to claim 9, wherein the at least one photoinitiator of formula (1) is as defined in any one of claims 2-4.   Colored and uncolored paints and varnishes, powder coatings, printing inks such as screen printing inks, offset, flexographic or ink jet printing inks, printing plates, adhesives, sealings, potting parts, dental compositions, foams, Compounds for molding, composite compositions, glass fiber cable coatings, screen printing stencils, for the production of three-dimensional objects by stereolithography, and as image recording materials, photoresist compositions, decolorizing materials, decolorizing image recording materials The method according to claim 9 or 10, for producing an image recording material using a material and a microcapsule. Formula (1) for photopolymerization of monomer, oligomer or polymer compounds containing at least one ethylenically unsaturated double bond

(Where
X is O, S or a direct bond,
Y is O, S or CR ₉ R ₁₀ ;
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of each other hydrogen, halogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₈ alkenyl, _phenyl, C 1 -C _{4 alkoxy,} C 5 -C ₇ cycloalkoxy, _phenoxy, C 1 -C ₄ - _alkylthio, C 5 -C ₇ cycloalkylthio, phenylthio, di _(C 1 -C ₄ alkyl) amino, di _(C 5 -C ₇ cycloalkyl) amino, N- morpholinyl, N- piperidinyl, or a group of formula (2)

Provided that one or more of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ or R ₈ is a group of formula (2);
R ₉ and R ₁₀ are independently of each other hydrogen, C ₁ -C ₁₈ alkyl, C ₂ -C ₁₂ alkenyl, C ₅ -C ₁₀ cycloalkyl, phenyl-C ₁ -C ₄ alkyl, phenyl, or Together with the C atom to which they are attached form a 5-, 6- or 7-membered ring,
R ₁₁ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₂ alkenyl, phenyl-C ₁ -C ₄ alkyl or phenyl)
Use of photoinitiator compounds.   13. Use according to claim 12, wherein the photoinitiator of formula (1) is as defined in any one of claims 2-4.   Colored and uncolored paints and varnishes, powder coatings, printing inks such as screen printing inks, offset, flexographic or ink jet printing inks, printing plates, adhesives, sealings, potting parts, dental compositions, foams, Compounds for molding, composite compositions, glass fiber cable coatings, screen printing stencils, for the production of three-dimensional objects by stereolithography, and as image recording materials, photoresist compositions, decolorizing materials, decolorizing image recording materials Use of the photopolymerizable composition according to any one of claims 5 to 8 for production of an image recording material using a material and a microcapsule.   A coated substrate having at least one surface coated with the composition according to claim 5.   An article comprising a polymerized or crosslinked composition obtained by curing the polymerizable composition according to any one of claims 5-8. In order to obtain the corresponding glyoxylic acid compound of the formula (1) as defined in claim 1, a halide compound (2a) or an oxalate compound (4a) or an anhydrous compound (5a)

Wherein R ₁₁ and R ₁₂ are independently of one another hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₀ cycloalkyl, C ₂ -C ₁₂ alkenyl, phenyl-C ₁ -C ₄ alkyl or phenyl. Yes,
Hal is a halide, preferably chloride)
A polycyclic aryl compound (1a) using

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently of one another, hydrogen, halogen, C ₁ -C ₄ alkyl, C ₅ -C _7. cycloalkyl, _phenyl, C 1 -C _{4 alkoxy,} C 5 -C ₇ cycloalkoxy, _phenoxy, C 1 -C ₄ - _alkylthio, C 5 -C ₇ cycloalkylthio, phenylthio, di _(C 1 -C ₄ alkyl) amino Di (C ₅ -C ₇ cycloalkyl) amino, N-morpholinyl, N-piperidinyl,
Provided that at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ is hydrogen;
X and Y are as defined in claim 1)
A process for preparing a compound of formula (1) as defined in claim 1 comprising the step of Friedel-Crafts acylation of

Images